Lubricant composition



United States Patent 0 LUBRICANT COMPOSITION Frank A. Stuart, Orinda, William '1. Stewart, El Cerrito, Warren Lowe, San Francisco, and Frank W. Kavanagh, Berkeley, Calif., assignors to California Research-Corporation, San Francisco, Calif., a corporation of Delawere No Drawing. Application April 21, 1958 Serial No. 729,560

45 Claims. (Cl. 252--42.7)

This invention relates to a novel lubricant composition, and it is particularly directed to the provision of a lubricant composition which is adapted to be employed in internal combustion engines.

With the refinements now being made in automotive and other internal combustion engines, a great deal of attention is being directed to the provision of a lubricant which will permit the engine to be operated at a high level of efiiciency over long periods of time. The pri mary fuiiction of the lubricant is, of course, to reduce friction and thereby not only decrease the wear on pistons, piston walls, bearings and other moving parts, but also increase theetliciency of the engine. Additionally, it is also a function of the lubricant to prevent the deposition of solid products on the piston Walls and other surfaces of the engine coming in contact with the lubricant. Such deposits seriously interfere with efficient engine operation for they accelerate piston ring and cylinder wall wear and also increase oil losses by p1ug ging the oil ring grooves. The troublesome deposits which form on the face of the piston and on the other walls of the combustion chamber, as well as on valves and spark plugs are also partially attributable in many cases to the lubricant, and especially to various of the metal-containing additives employed therein. It is of importance to eliminate or at least minimize the formation of all such deposits, and it is the basic object of this invention to achieve such a result.

To a minor degree, certain of the deposits formed on engine surfaces have their origin in the oil itself, that is to say, in the decomposition products of the oil. A more important, though still minor, source of engine deposits lies in the additives with which oils are conventionally supplied. This is particularly the case with metal-containing additives as, for example, the organic, metalcontaining salts which are incorporated in the oil to increase the detergency thereof, and the various metalcontaining compounds which are added to increase the lubricity of the oil and reduce piston ring and cylinder wall wear. Whenever oil is burned in the engine (as occurs with the oil film present in the cylinder wall during the combustion stroke) any metal-containing additives present in the oil may form an ash which is partially deposited out on the various surfaces of the combustion chamber and on those of the spark plugs and valves. Accordingly, it is a particular object of this invention to provide a lubricant composition which is compounded with metalor mineral-free detergents and wear-reducing additives.

While certain of the additives heretofore employed in oils (and to a lesser degree the oil itself) are partially responsible for deposits which form on engine surfaces, it is now recognized that the major source of such deposits or their precursors lies in the various aldehydes, acids, oxy-acids and other similarly reactive, partiallyoxidized combustion products of the fuel. These products are formed both under pre-ignition conditions as "ice well as during the combustion step proper, particularly during the period before the engine has reached operating temperature. Accordingly, under city driving conditions where the engine is repeatedly started in the cold condition and is seldom driven for a distance suflicient to reach the most efficient operating temperatures, the formation of partial oxidation products is particularly severe. Many of these partial oxidation products are carried down into the crankcase of the engine along with other blow-by gases, and since most are insoluble or only sparingly soluble in lubricating oils, they tend to separate from the oil and adhere to engine surfaces or form large droplets. In either case, under the elevated temperature conditions prevailing in the engine, these reactive monomers quickly polymerize to form solid masses which readily deposit out on the engine wall surfaces.

It is the practice in the art to prevent the formation of such deposits by adding to the lubricant a material normally referred to as a detergent. Insofar as is known, all the detergent additives which have been successfully employed prior to the present invention on a commercial scale are organic, metal-containing compounds such as calcium petroleum sulfonate, calcium cetyl phosphate, calcium octyl salicylate, calcium phenyl stearate, the barium salt of wax-substituted benzene sulfonate, or the potassium salt of the reaction product of phosphorus pentasulfide and polybutene. Various of these detergents act by reacting chemically with deposit precursors to form harmless compounds. Others act to prevent flocculation of coagulation of solid particles in the oil and maintain the same in a state of suspension as finely divided particles. Still others not only perform this dispersant function but also effect the solubilization or emulsification of the sparingly soluble monomers in the oil and thereby greatly reduce the rate of polymerization. In the latter case, such polymer materials as do then form within the body of the oil are smaller in size and can be peptized or dispersed in the oil much more readily than is the case with the large polymeric particles which are formed on exposed engine surfaces or in droplets lying without the oil.

Detergents capable of acting in the latter fashion are preferably employed wherever possible, particularly in automotive engines to be operated under city driving conditions. However, even among the metal-containing additives, few are available which are capable of solubilizing any appreciable amount of all the many types of polymer precursors which are carried into the oil from the fuel. Accordingly, it is a more particular object of this invention to provide a lubricant composition incorporating a metal-free detergent which is capable of solubilizing or emulsifying in the lubricant large amounts of all the various partial oxidation products of the fuel which are carried into the oil, and which is also capable of maintaining in suspension in the oil the various solid polymeric materials which are present therein.

The problem of piston ring and cylinder wall wear, especially the control thereof, is also one which is closely related to the composition of the crankcase lubricant. Aside from abrasive wear, which is caused by dust and dirt and can be remedied by suitable filtering and aircleaning means, a large part of the wear experienced by piston rings and cylinder wall is attributable to chemical attack by moisture and acidic products originating as byproducts of fuel combustion. In engines operated at optimum temperature levels, these combustion products are largely discharged through the exhaust and breather pipe. However, under the relatively cold conditions experienced in city driving, and especially at cylinder wall temperatures below about F., the moisture and acid products are condensed on the engine surfaces where they promote corrosive attack and are in a position to work past the piston and accumulate within the engine and in the crankcase oil. This difiiculty is one which the art has heretofore met most successfully by supplying the lubricating oil with additives such as the various metal salts of petroleum sulfonic acids and'other metal-organic compounds, especially those having a basic reaction. However, this practice has a disadvantage of adding still another metal-containing ingredient to the oil and therefore of increasing the deposit-forming characteristics of the lubricant composition. Accordingly it forms still another object of this invention to provide a lubricant composition containing a metalor mineral-free additive which effectively decreases the wear experienced by piston rings and cylinder walls, particularly during periods before the engine has become thoroughly warmed to' operating temperatures.

In'previously filed copending'patent applications of the present inventors, as hereinafter noted, the invention is based on the discovery that certain polyglycol substituted copolymers, which contain no metal component and therefore are substantially free of any ashgforming tendency, have the ability to impart excellent detergent and antiwear qualities to lubricating oils employed in internal combustion engines. In particular, these copolymers have the ability to solubilize in the oil large amounts of all the various partially oxidized combustion products of the fuels employed in internal combustion engines, while also having the ability of maintaining in a state of suspension any solid .polymeric products present in the oil. Additionally, the copolymeric additives effectively reduce the wear experienced by piston rings and cylinder wall surfaces even under themost unfavorable operating conditions such as. are experienced during the starting and warming up of the'engine. These additives have the advantage that they apparently do not' combine chemically with the various polymer precursors which are solubilized or dispersed in the oil, nor apparently do they act by a neutralization 'reaction'in counteracting the effect of the various acidic fuel combustion by-products. Accordingly, they are capable of giving excellent protection against engine deposits and wear over extended operating periods. Furthermore, the copolymeric additives of the polyglycol ester type are noncorrosive to the various bearing metals employed in engines.

Since the additives containing polyglycol groups differ in kind from any previously proposed for either detergent or antiwear purposes, it would have been surprising to discover that they were effective for any of the above purposes. The fact that they possessed not one but all of said qualities was altogether unexpected and could not have been predicted.

The-polyglycol additive of the present invention is a predominantly aliphatic hydrocarbon macro-molecule having polyglycol groups which comprises up to about 99.9% by weight of hydrocarbon oil-solubilizing groups selected from the class consisting of aliphatic and cycloaliphatic hydrocarbon groups of at least 4 carbon atoms each and at least about 0.1% by weight of polyglycol groups having at least 5 alkylene oxide units in each polyglycol group and from 2 to 7 carbon atoms in each alkylene oxide unit, said macromolecule having an average molecular weight of at least about 50,000 and a solubility in oil of at least 0.5% by weight.

The essential composition of the polyglycol additive as described above is the predominantly aliphatic hydrocarbon macromolecule having polyglycol groups. The aliphatic hydrocarbon portion provides the oil solubility to the additive and the polyglycol portion provides the polarity to the additive. The combination of these portions in the macromolecule results in an additive having the detergent and antiwear properties as noted above. However, other groups characteristic of macromolecule lubricating oil additives, including other polar groups besides the polyglycol groups, may be'incorp'orated within which A is an organic macromolecule group, preferably an aliphatic hydrocarbon group, and R is an aliphati-c or cycloaliphatic hydrocarbon group of at least 4 carbon atoms or mixtures thereof, L and L are suitable divalent linking groups, PG is a polyglycol group having at least 5 alkylene oxide units and from 2 to 7 carbon atoms in each alkylene oxide unit and O is a polar group other than the polyglycol group. The letters x, y and aim the formula are integers showing the number of times the bracketed portions occur.

Illustrative polyvalent linking groups of the type mentio'ned in the preceding paragraph include alkylene groups such as methylene -CH oxy O--, carbonyl H imino carbonyloxy Ni J-O, sulfide -S' phosphonyloxy -P and imino --NH- groups and combinations thereof with alkylene groups of from 1 to 7 carbon atoms each.

Illustrative polar groups other than the polyglycol group include the free carboxyl group the amidocarbonyl group ((INH2) hydroxy and amino-substituted alkylamide groups (-CNH-ROH and where R is an alkylene group, preferably of not more than (carbon atoms), hydroxy and amino-substituted alkyl ester groups, heterocyclic nitrogenous groups, such as pyridyl, pyrollidyl and carbazolyl groups, epoxy groups, such as the glycidyl group, and cyano groups.

The predominantly aliphatic hydrocarbon macromolecule of the invention due to its high molecular Weight of 'at-least.50,000 is most suitably a polymeric type com pound. For example, satisfactory polyglycol additives are obtained by attaching polyglycol groups to ethylene, propylene or isobutylene polymers by means of suitable groups. Particularly suitable hydrocarbon macromolecules areobtained by copolymerizing (A) oil solubilizing olefinsof 2 to 30 carbon atoms or monomeric compounds having a polymerizable ethylenic group and containing a hydrocarbyl group of from 4 to 30 aliphatic carbon atoms, (B) polyglycol monomeric compounds having a polymerizable ethylenic linkage and a polyglycol group containing at least 5 alkylene oxide units in which each alkylene oxide unit has from 2 to 7 carbon atoms and, optionally, (C) monomeric polar compounds having a polymerizable ethylenic linkage and a polar group of the type mentioned above.

The oil-solubilizing monomer portion of the polymeric additives of this invention can be any compound having at least one ethylenic linkage C= together with at least one substituent group which contains an oil-solubilizing hydrocarbyl group of from 4 to 30 aliphatic carbon atoms, and which is characterized by the ability to copolymerize through said ethylenic linkage with the polar monomer referred to above in the presence of a suitable catalyst. Alternatively, the oil-solubilizing aliphatic radical can be introduced into the copolymer, as will hereinafter be more fully described. This aliphatic radical, whether present in the original monomer or introduced into the copolymer, imparts oil solubility to the polymer and is preferably a branched or straight-chain alkyl radical or a cycloalkyl radical such as butyl, isobutyl, n-pentyl, n-hexyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, cyclohexyl, 4-ethylcyclohexyl, or the like, or an alkenyl radical such as oleyl, ricinoleyl, or the like, wherein the ethylenic double bond has substantially no copolymerizing tendency. Oil solubilizing monomers of this general character are well known in the art and are frequently employed as the oil-solubilizing portion of copolymers which are added to lubricating oils to improve the viscosity index and pour point characteristics thereof. They include such materials as olefins and ethylenically unsaturated others, esters, ketones, aldehydes, and the like.

The oil solubilizing monomeric compounds of component (A) may also be illustrated by the following general formula:

in which R and R are members of the group consisting of hydrogen and hydrocarbon radicals of from 4 to 30 carbon atoms, at least one of which contains an aliphatic hydrocarbon group of from 4 to 30 carbon atoms as described above, G and G are members of the class consisting of oxy l carbonyl i and carbonyloxy i-0 or O(]) groups and combinations thereof with not more than two alkylene groups of from 1 to 7 carbon atoms each, and n and n are 0 or 1. When R and R are hydrocarbon radicals, they may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl in structure, as illustrated by radicals such as Z-ethylhexyl, cyclohexyl, hexenyl, cyclohexenyl, phenyl, naphthyl, tertiary butylphenyl benzyl, etc., with the preferred radicals being as previously mentioned.

Representative oil-solubilizing olefins and monomeric compounds of the aforementioned types which can be employed to form the copolymeric additives of the present invention include the following:

0 LE FINS Ethylene Hexadecene-l Propylene Cyclohexene Butened Octadecene-l Isobutene t-octylcyclohexened Pentene-l 3-phenylhexadecene-l Hexene-l -Qctylstyrene Zethylhexene-l mylcyclohexane DX- and triisobutylene 2-hexadecylbutadiene-1,3 Tripropylene p-Tertiarybutylstyrene Dodecene l ETHERS Vinyl n-butyl ether Propenyl zethylhexyl ether Vinyl Z-ethylhexyl ether Crotyl noctyl ether Allyl n-butyl ether Isopropenyl dodeeyl other Allyl isobutyl ether Allyl eyelohexyl ether Allyl esters of babassu acids Allyl esters of lard acids Allyl nnphthennte Methallyl caproate Math allyl naphthenate Methallyl ricinoleate Methallyl p-octylbenzoate Methnllyl oleate Methallyl cyclohexane cnrboxyle Methallyl palmltate Crotyl oleate Crotyl naphthenate a-Methylerotyl palrnitate l-propenyl uaphthenate l-propenyl elaidate Dodecyl acrylate Hexadecyl methacrylate Isooutyl a-deeylecrylate Vinyl p-n-octyl beuzoato Allyl 3,5-diisobutyl benzoate l-decenyl butyl ether l-eicosenyl decyl ether n-Butyl 2-eic0senoate p-Tert.

maleate p-Hexadecylphenyl Z-ethylhexyl maleate o-Tolyl Z-octadecylcyclohexyl maeate O-Nonylphenyl-hexadecyl maleate Dihexadecyl maleate Di-rnethylcyclohexyl maleate Mono-Z-ethylhexyl maleate Di-2-ethylhexyl maleate Dl-dodecyl maleate Di-dodecyl iumarate Di-dodeeyl mesaconate Di-dodecyl eitraconate o-Tolyl octadecyl itaconate Mono-hexadeeyl itaconate Isopropenyl palmitoleate i-decenyl laurate l-hexadecenyl myrlstate amylphenyl ostadecyl Cyclohexyl methacrylate Although any of the oil solubilizing compounds described above will give effective copolymer compositions for lubricant compositions in accordance with the present invention, higher alkyl esters of mil-unsaturated monocarboxylic acids of from 3 to 6 carbon atoms having alkyl groups of from 8 to 30 carbon atoms are most preferred, both for availability and effectiveness of copolymers prepared from them. Representative acids of this type are the acrylic, methacrylic, crotonic, tiglic, angelic, a-ethylacrylic, a-methylcrotonic, a-ethylcrotonic, fi-ethylcrotonic, fi-propylcrotonic, and hydrosorbic acids and the like. Even more desirable are the alkyl esters of acrylic and methacrylic acids containing from 10 to 20 carbon atoms in the alkyl groups, since they are found to provide highly superior polymers for the lubricant compositions of the invention and are obtainable in commercial quantities.

Various copolymers employing representative oilsolubilizing monomers of the foregoing types were prepared to illustrate the oil solubilizing effect of the monomers on the resultant copolymers. The solubility of the copolymers in oil and their suitability as lubricating oil additives were demonstrated by incorporating the copolymers into lubricating oils. The lubricant compositions thus obtained were tested to determine their detergency and deposition properties. The results of these tests are given in Table I below.

In the tests the base oil, unless otherwise indicated, is a solvent-refined, wax-free, SAE-30 grade mineral lubricating oil having a viscosity index of which is derived from California waxy crude. Various amounts of the copolymers are incorporated into the oil as indicated in terms of percent by weight.

The piston varnish ratings of the lubricant compositions were obtained by the standard FL-2 test procedure as set out in the June 21, 1948 report of the Coordinating Research Council. In this test the lubricants in a 6-cylinder Chevrolet engine, using a low-grade gasoline especially prone to cause engine deposits. At the end of each test the engine was dismantled and the detergency or deposition properties of the lubricant compositions were determined by examining the engine deposits on the piston and visually rating them as to the amount of 7 piston varnish present. The piston varnish ratings of the compositions are given in numerical terms on a scale of' l0with l0 representing the complete absence of'depi5s'it's;

The deposition characteristics of the lubricant compositions containing the copolymeric additives were also determined in the lacquer deposition test. In this test typical engine fue'l combustion products were passed into the lubricant compositions and the ability of the lubricant compositions to solubilizeand retain the lacquer-forming materials was observed by weighing the amount of lacquer deposits fo'rrned on a fresh iron catalytic surface for a, standard perio'dtof time. The lacquer deposit of the lubricant composition isftaken as the number of milligrams'deposit' onfth'e' metal surface, and may be correlated directly to the piston varnish rating obtained in the standard FLA-'2 test procedure outlined in the above para- Both the FL-2 test procedure and the lacquer deposition 'tesf'are more fully described in the disclosure which follows with'regard to the particular lubricant composition of the present invention.

the particular polymeric additives of the inventign'; have the above-described essentialj characteristics, Poly-l 2 alkylene glycols and,,their' aIkyLethers haying molecular; weights between 220 and 30,000. are preferred .Such glycols may be obtained by polymerizing l,2-alky l e n oxides or mixturesthereof in the presence jot acata lysg and a suitable initiator for the reactionsuehaslwater, monohydric alcohol in the case of the alkyl Qthers meQ captans and the like. The preparation 10fp'olygly'jc'qol compounds of thi s type hasbeen fully .dtscribedlheretofore in US. Patents 2,448,664and2,451,139,,for ,example, and, therefore, requires 'nodetailed discussion here.

For present purposes, ,themost suitable poly; l,2 ;al lgy l ene glycol group's'are' those derived fr0mf,e thylene oxide or from l,2-prop'ylen'e oxide or mixtures thereofiand Ttheir, alkyl ethers of l: to 18 carbonatorns per alkyl group which have molecular weights or .vaverageirmol'ecular weights between about .220. and. I 30,000.. preferablybe; tween about 400 and 10,000. These polyalkylene glycol groups are found'to provide" the most effective detergent and .wear inhibiting compositionsl The following polyalkylene glycol groups containing Table 1 Ratio of (1) .-..1 Piston monomer. Lacquer ,yarn sh to (2) mon- Plston- -deposit rating-(es- Lubricant composition omerto (3) :varnish- (millln: timated monomer, rating grams) horn,

etc. lacquer- Y deposit) 3.0%(1)tridecylmethacrylate fl) octadeeyl methacrylato, (3) monododecyl ether of 1 hexadecacthylen'e glycol I methacry fl 10/6/1 8. 4 2.8% 1)vinyl stea'rate, (2) maleic anhydride, (3) monododecyl ether of pcntaethylene glycol P methacrylate, (4) methacry e /1/2/1 325 6. 0 2.8% (1) hexene-l, (2) dodecyl methacrylate, (3) methacryhc acid, (4) monododecyl U ether'ot eicosaethylene glycol e methacry 25/25/114 400 5:5 2.8%(1) di-Z-ethylhcxyl fumarate, (2) octadecene-l. (3) crotonie acid, (4) monotndecyl ether of decaethylene glycol d mcthacry 25/25/812 570 4. 0 2.8% (1) allyl ethyl ether, (2) vinyl stearate, (3) itaconlc 801d, (4) monododecyl other oidecaethylene glycol d crhtnnafe 14/50/7/3 1.5% (1) dodecyl acrylate, (2) monododecyl ether of decacthylene glycol d acrylate,

(3) acrylic acid 780/9/1 5. 6

Ir 1,140 Neutral Mineral Lubricating Oil from solvent-refined waxy California crude.

Polyethylene glycol of 704 M.W. b Polyethylene glycol of 220 M.W. e Polyethylene glycol of 880 M.W. Polyethylene glycol of 440 M.W.

From the above test data it will be seen that all of the various oil-solubilizing monomers representative of the aforementioned types were elfective in the production of useful, copolymeric lubricating oil additives which are capable of preventing deposits from lubricant compositions under typical engine operating conditions. These monomers, as previously described, constitute a definite, recognized class of compounds which have been used heretofore in the art in the production of polymeric lubrieating-oil additives of the nonpolar type, such as VI improvers and pour point depressants. Although the results demonstrate beyond any reasonable doubt the suitability of the diiferent oil-solubilizing monomers within the terms of the description in the production of oil soluble copolymers, it should be understood that the efficacy of each individual class of copolymers as detergents is primarily dependent upon the polyglycol group and its relationship --to the rest of the copolymer.

Briefly described, the polyglycol groups of the predominantly aliphatic hydrocarbon macromolecule additives-according to the invention are essentially characterized by the presence of at least 5 alkylene oxide units each with alkylene groups of from 2 to 7 carbon atoms each as previously mentioned. The end of the polyglycol group other than that linked to'form the macromolecule may behydroxyl or it mayhave other terminal groups, includingpclargroups g v ,.T he polyalkylene glycols of the polyglycol monomeric compounds noted previously as the- (B) components offrom 2 to 7 carbon atoms in each alkylene group" are illustrative of the types described above.

The predomin n aliphatic hydrocarbon use cules having polyglycol groups in accordance with the invention as already mentioned are most suitably polymeric additives. Although the polyglycol groups are operative Without regard to any specific mode of attachment to the hydrocarbon portion of the additive, particularly suitable additives are obtained by copolymerizetion of an oil-solubilizing monomer (A) with a polyglycol (B) monomer having a polymerizable ethylenic linkage and a polyalkylene glycol group of the abovedescribed type. More particularly, suitable polyglycol monomers are characterized by a hydrocarbon portion having a polymerizable ethylenic linkage which is connected to the polyglycol portion by a linking group of the aforementioned description.

Illustrative polyglycol monomeric compounds are the monoesters of 04,]3-UIISHtUI'3t6d monocarboxylic acids of 3 to 15 carbon atoms and aJB-UHSQUJI'MCG, a,,8-dicarboxylic acids of 4 to 12 carbon atoms. The preferred monocanboxylic acids are those containing from 3 to 8 carbon atoms and more particularly acrylic and methacrylic acids. The preferred dicarboxylic acids contain a total of from about 4 to 8 carbon atoms with maleic acid being particularly preferred.

Also included as suitable polyglycol monomers are the polyglycol amides of unsaturated monocarboxylic acids and dicarboxylic acids of the above-described types. Such monomers are obtained when the amide of an unsaturated acid is used as an initiator in the polymerization of the 1,2-alkylene oxides or mixtures thereof as mentioned above. The methacrylamide initiated polyalkylene-glycol is an example of these monomers.

The vinyl and allyl monoethers of polyglycols are also satisfactory polyglycol monomers. Such ethers are obtained by the reaction of acetylene with preformed polyglycol or by the use of unsaturated alcohols such as allyl alcohol as initiators in the polymerization of 1,2- alkyleneoxides or mixtures thereof. Examples of these monomers are allyl alcohol initiated polyethylene glycol and methallyl alcohol initiated polyethylene gycol.

Other types of monomers with other kinds of linking groups such as the phosphonyl and sulfonyl groups referred to above are also satisfactory for the polyglycol monomers.

In the preferred copolymeric type polyglycol macromolecules of the invention, the polyglycol ester monomers are particularly suitable. These monomers have a general structural formula r r t R O=CCO-(R -O)HRe where R R and R are hydrogen atoms or C -C alkyl radicals, the R s are 1,2-alkylene radicals of 2 to 7 carbon atoms, n is an integer greater than 5, and R is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, the substitutent groups here contemplated being the polar groups if -ooo11, C-OR OR -No,, -sn,

if if on7, NR7-RH, or owhere the R s and R s are hydrogen atoms or hydrocarbon groups. For present purposes, however, a more preferred group of polyglycol ester monomers, previously referred to as (B) monomer components, is made up of those compounds wherein, in the above structural formula, R and R represent hydrogen atoms, R represents hydrogen or a methyl group, the R s are ethylene or propylene groups, and R is hydrogen or an alkyl group of from 1 to 18 carbon atoms.

The optional monomeric polar compounds previously designated as the (C) monomers, as already discussed, are monomers having a polymerizable ethylenic linkage and a polar group. Many such monomeric polar compounds for use in the production of polymeric detergents for lubricating oils have been recognized and may be incorporated in the additives of the present invention without adversely afiecting the superior detergent and antiwear properties.

Our copending application Serial No. 574,635, filed March 29, 1956, as mentioned above, describes the inclusion of free unsaturated monocarboxylic acid monomers in polyglycol type copolymers. The monomer of (A) dodecyl methacrylate (B) dodecyl ether of polyethylene glycol monomethacrylate in which the polyethylene glycol has a molecular weight of 1600 and (C) methacrylic acid is illustrative. Copending application Serial No. 645,887, filed March 14, 1957, describes polyglycol containing copolymers including free dicarboxylic acid monomers or their anhydrides such as the copolymer of (A) allyl stearate and didodecylmaleate (B) dodecyl nonaethylene glycol maleate and (C) maleic anhydride. Copending application Serial No. 645,888, filed March 14, 1957, describes polyglycol copolymers including amino and hydroxy-substituted alkyl esters of unsaturated carboxylic acid as illustrated by the copolymer of (A) dodecyl methacrylate (B) dodecyl ether of polyethylene glycol monomethacrylate in which the polyethylene glycol has a molecular weight of 1600 and (C) ethylene-glycol monomethacrylate. Copending application Serial No; 646,524, filed March 18, 1957, describes polyglycol copolymers including amide and amine salts of unsaturated acids which amides and amine salts may contain hydroxy alkyl and monoalkyl substituents as illustrated by the copolymer of (A) dodecyl methacrylate (B) dodecyl ether polyethylene glycol monomethacrylate in which the polyethylene glycol has a molecular weight of 1600 and (C) N,N-dimethyl amino propyl amine methacrylate.

Although the optional polar groups other than the polyglycol group of the additives of the invention are incorporated into the macromolecule by various suitable methods known to the art, the preferred additives are copolymers containing copolymerized polar group monomers other than the polyglycol monomers referred to above. In addition to the free carboxylic acid monomers and amino and hydroxy-substituted alkyl esters, amides and amine salts of unsaturated acids of the copending applications already noted, suitable polar group monomers besides the polyglycol monomers include the heterocyclic nitrogenous monomers such as vinyl pyridine, vinyl pyrollidone and vinyl carbozole. Epoxy ether and ester monomers such as glycidyl vinyl ether and glycidyl methacrylate are also illustrative of suitable polar monomers in combination with the polyglycol group monomers. Various alkyl derivatives of the polar monomers are likewise satisfactory as in the case where lower alkyl groups are substituted on the ring of the heterocyclic nitrogenous monomers. Combinations of the aforementioned polar groups are also included, as for example where both a vinyl pyrollidone and a dialkyl aminoalkyl ester of an unsaturated carboxylic acid are used together with the polyglycol monomer and the oil-solubilizing monomer.

In preparing the polyglycol additives of this invention, it is important to obtain a final product which is oil soluble, i.e., which is soluble in the petroleum or other lubricating oil employed, to the extent of at least 0.5%, and preferably 2% or more by weight. Since the various oil-solubilizing aliphatic hydrocarbon groups, for example, the oil-solubilizing monomer components of the polymeric type macromolecular polyglycol additives, differ somewhat in their oil-solubilizing characteristics, preliminary tests are made with the additive to determine whether the relative proportion of aliphatic hydrocarbon, or of oil-solubilizing monomer compound in the copolymer, is high enough to impart the desired degree of oil. solubility;- If the solubility in oil is unduly low the proportion of aliphatic hydrocarbon groups is easily in creased to raise the oil solubility to the desired level,

ni cp l me Qtthe t n ei in hi htt at neomb i ath r f s fq r in th .gqiw yn e. th i q ub i ylh r f an nofinal aremed cd YfifiFIiil: inga portion of said carboxyl groups with a higher alco hol, e.g., a C or higher aliphatic alcohol such as 1 1- octanol, 2 -ethylhexanol, decanol, dodecanol (lauryl alco th li en atn cw jvcr. sat sf ry oi -sol b i antiwear and detergency properties are obtained with polyma r t et or. oi -s lub z n q m s m @92 stitutes from about 40 to 99.9. weight percent of the overl rol m c mi qsit c i h th (B), MQMH. P a po y ly l ummer clp a p a m n m 0 Re nt s re ti sat tal. f .from 19 9- We ht Perc nt o then ia .qqm cs tignr re be n i a l cases at least one and usually several monomer units of aid .03) q ysl wl. 9. 1??? com nent t ppl sn, xpre s d. at eewi e tt ew P a onq erfiut t tithe cq'pq t e -p yyco co o en -c ns tutes twi 01 v3. We lia mwh he RQP F Q P F g im vn n g st mt o 0 t .W aht1 s B r rt l n eram9 xp o at ry r se c suppq 'tadb engine e t t da a preferredrangescan be established within the. aforesaid ranges for particular polymers and classes QfLp oIymerS coming within thescopeof this invention. Thus, with copolymers of (A), a higher alkyl methacrylate (e.'g. au v .m ltha r a (B) try a e 9 ,me liae e f a PQ Y Y I a ve lar a l b y sae g ol. r a rnon'oalkyl ether oi said glycols, or mixture of said glycols or glycol others, or a polyglycol monoethen where the glycols are ,of the molecular. weights previously speci fied for these compounds, and (Qlotherpolar monomers of the previously describedtypes, there preferab,ly is employed from 80 to 96 weight percent oftheoilsolubilizing, (A) component. The balance or polar portion of the polymer, takenonthe basis of l00 w eigl:it"per n polar p t is m de u r mfii t JOO. w i ht pe cent of the (B) component and 65 I00 weight percent of the (0) component. V, 4 p,

,Although efiectivecopolymers according to the invention are obtained with proportionsof oil-solubilizing (A) monomer units and polar (l 3 and (C) monomer units within the aforementioned ranges, it hasbeen noted that in a preferred p cation of he p m t club i ati s detergent i es he ptcs itinr nt q ming al i i so a a ptimum e i nship a p ars. t exi w e he. ota numbe pt p ubil zine aliphat carbon atoms and thetotal, number of: polar groups qvith in the molecule. This optimum relationship vvhicli is termed fpola'r balance for convenience, is expressed by the formula and excluding aromaticlring carbon atoms and the carboniatoms of carbonyl groups,

The polar balance of a givencopolyn'fer according to the abovefo'rmula is equal to th'esurn of theln'u'mberof each type 'of' polar". group multiplied by. its polarityiconstant, said sum being-thendividd byzth'e number of solubilizingaliphatic carbon atoms. Fol-best performance,

12 th no arhalans ap rqxirn t y. 1- How r. v ry ftet e s m yma h ic tirep et r additives may have polar balances in the range from 0. l 5 to 3.00. .Thomacromolecules employed in the compositions of this invention canbe prepared by any one of several me hpq ma tk own in t rt A te e, the oil-solubilizing groups, the polyglycol groups and the option'al polar groups of the macromolecules areattached invarious ways. In the case of theessential polyglycol groups there are three general methods of attachment. (1 )Il'1e polyglycolgroup may be incorporated by reactionwith a preformed polymer containing reactivecen; ters such asjree carboxyl groups. (2) Thepolyglycol group may also be introduced as a polymerizablemonomer prepared by (a) reacting a polyglycol compound with a reactive monomer such as methacrylylchloride or methacrylic acid, or .(b) initiating alkylene oxide poly merization with a suitable compound containing a poly merizable double bond, suchas allylalcohol. (3) The polyglycol group may also be incorporated'in a similar fashion by initiating thealkylene oxide polymerization with a preformed polymer containing reactive centers as described in 1). In the caseof the oil-solubilizing groups and the optional polar groups themethods of attachment would be the same except for the alkylene oxide polymerization. v

Thus, one may polymerize a mixture of the desired monomer components to form the desired polymer. Satisfactory copolymers are also obtained, however, by starting withsuitable precursor compounds, with the desired monomer unitsthen being formed by the appropriate treatment of the resulting polymeric intermediate product. Thus, o nemay first copolymerize a givenoil-solubilizing compoundsuch as an alkyl methacrylate with a suitablejacid component such as methacrylic acid or maleic. anhydride and some other polar component such as pyrollidone; the resulting polymer is then reacted with a polyalkylene glycol whereby a portion or all of the free -COO H groups in the polymer intermediate becomemonoester-linked to the polyalkylene glycol.

The general principles of preparation outlined above are applicable to'all types of macromolecules according to the invention. Other possible variations in the nature of the reactants and in the selection of asuitable reaction path would obviously suggest themselves to those skilled in theart. y

When the polymeric additive of this invention, ora suitable polymeric intermediate, is to be prepared by reaction of monomeric components, said polymers can be prepared by conventional bulk, solution or emulsion methods in the presence of an addition polymerization initiator. .Preferably, however, the copolymerization is effected in an inert organic solvent such as benzene, toluene, xylene or petroleum naphtha in the presence of a free radical-liberating type of initiator such as a peroxy compound, for examplejbenzoyl peroxide, acetyl peroxide, tert. butyl hydroperoxide, di-tert.' butyl peroxide, dibenzoyl peroxide, or di-tert. amyl peroxide, or an azo initiator such as 1 ,l'-azodicyclohexane-carbonitrile or a,a'-azodiisobutylronitrile. The catalyst, or polymerization initiator, can be employed in an amount of from about 0.1 to 10%, with a preferred range being from 0.10 to 2%. If desired, the catalyst can be added in increments as the reaction proceeds. Likewise, additional portions of the solventcan also be added from time to time in orderito maintain the solution in a homogeneous condition. The temperature of copolymerization varies from about to 30091 withthe optimum tcmperature for any given preparation depending on thenature of thesolvent, the concentration of monomers present in the solvent, the catalyst, and the duration of the reaction. Much the same conditions are employed when the copolyfnerizationis efiected in bulk rather than in the presence of an'inert solvent. a Other types of polymeric macromolecules within the scope of the invention as described above include the condensation polymers such as linear polyamides and polyesters having linked thereto suitable oil-solubilizing groups, polyglycol groups and polar groups of the aforementioned kinds. Such polyamides and polyesters are obtained by the well known condensation reactions of polybasic acids, polyamines, polyhydric alcohols, amino acids, amino alcohols, and the like. For example, the condensation of tartaric acid with ethylene diamine gives a linear polyamide having hydroxyl groups along the linear chain which may be used to introduce appropriate oil-solubilizing groups and polar groups.

The additives of the invention have apparent molecular weights as determined by standard light scattering methods of at least 50,000. For practical purposes, molecular Weights of from 100,000 to 1,000,000 are most suitable from the standpoint of viscosity and other physical characteristics of the polymeric additives.

Typical methods for preparing the polyglycol polymeric type additives which can be employed with success as detergents and antiwear additives in lubricant compositions according to the invention are given in the following examples.

EXAMPLE I In this operation a homopolymer of dodecyl methacrylate (Acryloid 710, a product of Rohm & Haas Company) was employed as the starting material from which was prepared a copolymer intermediate of dodecyl methacrylate and methacrylic acid. Tlze preparation was as follows: A solu ion of 14 gramsof potassium hydroxide in 300 cc. of 2-ethylhexanol was prepared, and to this solution was added 800 cc. of a 40% solution in mineral oil of the methacrylate homopolymer, this amount of KOH constituting a slight excess over that theoretically required to effect the desired saponification of approximately 12% of the ester groups present in the polymer. The resulting solution was heated to 320 F. and maintained at this temperature, with stirring, for hours. To this solution was then added 50 cc. of benzene along with a 50% excess of 6NHC1 over the amount theoretically required to liberate the free carboxyl groups from the corresponding salt. The acidified solution was then refluxed for two hours, after which it was cooled, diluted with ethyl ether, and water washed (along with a small amount of ethyl alcohol to break the emulsion) until neutral to litmus. The ether and dodecyl alcohol present in the solution were then distilled off, leaving as the oil-soluble residue a copolymer of dodecyl methacrylate and methacrylic acid wherein said components were present in a monomer ratio of 7.5 :1, respectively. 140 grams of the resulting polymer intermediate were then dissolved in 250 grams of xylene and 60 grams of benzene, and to the resulting solution was added 60 grams of a mixture of polyethylene glycol compounds consisting of major portions of nonaethylene glycol and having an average molecular weight of about 400, together with one-half gram of the esterification catalyst p-toluene sulfonic acid. This mixture was reiluxed at 270 F for 10 hours, after which a sufficient quantity of solvent was distilled off to raise the reflux temperature to 335 F., with the refluxing being continued for three hours at this temperature. The reaction mixture was then cooled and dissolved in an equal volume of benzene, from which solution the polymer was then precipitated out by the addition of five times the volume of a 4:1 acetone-methanol mixture. This polymer incorporated dodecyl methacrylate, methacrylic acid and polyethylene glycol monomethacrylate monomer units in the approximate proportions of 7.5:085:0.15, respectively. The viscosity blending characteristics of this product are substantially the same as those of Acryloid 710, indicating little change in molecular weight. In FL-Z tests, this polymer had an average piston varnish rating of 7.5. Further, the wear sustained by the piston 14 rings during this test was found to be but 2.6 mgs./hr'. as compared with a value of 5.5 mgs./hr. for the base oil alone.

EXABELE II g. of (0.5 mole) of vinyl stearate, 2.7 g. (0.021 mole) of itaconic acid, 14.8 g. (0.021 mole) of tridecylcapped polyethylene glycol methacrylate (molecular weight 708), and 200 cc. of butanone were charged to a three-necked reaction fiask fitted with a stirrer, thermometer, reflux condenser, and dropping funnel. The mixture was stirred and heated to reflux temperature, 188 F. A solution of 3.4 g. of benzoyl peroxide in 30 cc. of butanone was added during a period of 2 hours. No apparent thickening occurred during this time. On the removal of cc. of solvent, polymerization proceeded. The temperature was raised to 220- 225 F. and kept at this temperature for 2 hours. 1.7 g. of bulk catalyst was then added in small installments over a period of an hour. Additional thickening occurred on stirring the mixture at 220 F. for another 3 hours. 700 cc. of benzene was added to the mixture, and the polymer was precipitated with 5 volumes of methanol. The recovered product was taken up in mineral lubricating oil to give 144 g. of polymer as a 52% concentrate. Analyses of the concentrate indicated that the polymer contained vinyl stcarate, itaconic acid, and tridecyl ether of decaethylene glycol methacrylate in a molar ratio of approximately 68:4:3.

EXAMPLE III 75.5 g. (0.3 mole) of octadecene, 63 g. (0.3 mole) of di-Z-ethylhexyl fumarate, 8.2 g. (0.095 mole) of crotonic acid, and 16.3 g. (0.23 mole) of tridecyl-capped polyethylene glycol methacrylate (molecular weight 708) were charged to a polymerization reactor as described in the preceding example. The mixture was stirred and heated to 220225 F. with stirring. Bulk benzoyl peroxide was added intermittently in 0.8 g. installments during the course of 7 hours. The mixture was then kept at 194 F. for a period of 88 hours. The product obtained above was stripped to 425 F. at 1 mm. mercury to remove unreacted crotonic acid, octadecene, and di-2 ethylhexyl fumarate. 136 g. of polymer was obtained which was shown by analysis to contain octadecene, di- Z-ethylhexyl fumarate, crotonic acid, and tridecyl ether of decaethylene glycol methacrylate in a molar ratio of 10:15 :3:1.

EXAMPLE IV A three-necked flask fitted with a stirrer, thermometer, reflux condenser, and dropping funnels was charged with 29.6 g. (0.35 mole) of hexene-1. The monomer was stirred and heated to reflux, 146 F. A monomer mixture comprised of 89 g. (0.35 mole) of lauryl methacrylate, 1.2 g. (0.014 mole) of methacrylic acid, and 61.2 g. (0.059 mole) of dodecyl-capped polyethylene glycol methacrylate (molecular weight 1034), in 30 cc. of henzene was added to the refluxing hexene simultaneously with the addition of a catalyst solution. After the addition of 100 cc. of the monomer mixture and approximately 0.45 g. of benzoyl peroxide in 5 cc. of benzene over a period of 2 hours, no polymerization was observed.

During the course of addition, the temperature gradually rose, and after another two hours the maximum temperature reached was 187 F. Considerable thickening oc curred during this time and it was necessary to add xylene diluent in small portions at intervals to facilitate stirring. The mixture was kept at 190 F. for another three hours. At this point 177 g. of lubricating oil was added. The solvent and unreacted hexane, lauryl methacrylate and methacrylic acid were distilled from the mixture to give 140 g. of polymer as a 44% concentrate. The polymer was shown by analyses to contain hexene, lauryl methacrylate, methacrylic acid, and dodecyl-capped polyethylene glycol methacrylate in a molar ratio of 17:25:224.

action mix had stood at 60 C. for 4 hours.

EXAMPLE v j 119' kg. at phenol was mixed with 4 kg. 6f polyis cbutylcn'e having an average molecular weight or about400.

The polyisobutylene corresponding roughly to heptaisobutylene. To this mixture 90 g. of a boron trifluoride phenol complex was added to catalyze-the alkylation. An additional 90 g. of catalyst was added after the re- I The-heatmg was continued for another 3 hours and 2:5 liters of a 10% solution of potassium carbonate was then added to the mixture. This mixture was stirred for half an hour,

after which the potassium carbonate solution was with- .drawnand the alkylated phenol was washed with hot water until the water washes were neutral. The mixture was then stripped of water and other volatile material by h'eating to 320 F. under a vacuum of 3 inm. of'rne rcury. The yield of washed product was 4215 grams and the equivalent weight was 620.

4100 g. of the alkyl phenol obtained above was mixed =witlr21- g. of sodium hydroxide and the mixture added to-a bomb which was heated to 100 C; 415 g: of ethylene' oxide was charged to the bomb. This addition of ethylene oxide was carried out over a'pe'riod of 1 /2 hours in order to maintain the temperature of the exolate ester by reaction with methacrylic acid. 400 g. of 'the alkylphenoxyethanol, 215 g. methacrylic acid, ;400 cc. of benzene, 5 g. of hydroquinone and 3 cc. of sulfuric acid were mixed and heated under reflux at"about200 F. for about 20 hours. The theoretical ameum'er water was evolved. The contents of the vessel were filtered and stripped at 400 F. under 6 mm. of mercury pressure. The stripped product was washed with sodium hydroxide and then with water until the water was neutral.

It was then reheated to 220 F. under a pressure of 6 mm. of mercury to remove final traces of water. 'The yield was about 400 g.

100 g. of the alkylphenoxyethyl methacrylate obtained above, 5 /2 g. of methacrylic acid, 30 g. of dodecyl ether of decaethylene glycol methacrylate and 1.4 g. of benzoyl peroxide were charged to a flask and blanketed'with an inert atmosphere of nitrogen. Benzene was added to reduce the viscosity and the contents of the flask refluxed at about 197 F. for 3 /2 hours. Methanol was then added to the benzene solution to precipitate a viscous polymer product. The separated polymer was admixed with a mineral lubricating oil having a viscosity of 150 SSU at 130 F. The yield of lubricating oil polymer concentrate was 245 g. The polymer was a copolymer of heptaisobutylene-phenoxyethyl methacrylate-metha crylic acid-dodecyl ether of decaethylene glycol methacrylate with a ratio of 20:2:5.

Other polymers illustrative of the compositions of the invention were prepared according to the procedures outlined in the above examples. These polymers are referred to in the tables which follow where they are described with respect to the particular monomers and mole ratios employed.

In general, excellent detergent and antiwear properties can be imparted tolubric'ating oils by dissolving therein a quantity of from about 0.1 to 10% by weight of the polymers of the type described above, although a preferred range is from'about 1 to 5% by weight. On the other hand, since the polymers of this invention are unusually compatible with mineral and other lubricating oils in substantially all proportions, as much as 75% of the present polymerie additives can be dissolved in asuitable lubricating oil for the purpose of preparing a con- Qentrate capable of diluticnwith lubricating oils and the e'j fir pare j the anar "lubricant composition. Such con cer 1trates-,jwhiclrjnay also contain other additives in desired amounts and which normally contain at least 10% of the po1yme'r,"compr ise a convenient method for handling the" polymer and maybe used as a compoundingagent for lubricants in general.

The polymeric additives of this invention can be used with good efiect inthe case of any one of a wide variety of oils of lubricatingviscosity, jor'of blends of such oils. Thus; the base oil can be a refined Pennsylvania or other paraffin base oil, a refinednaphthenic base oil, or a synthetic hydrocarbonor nonhydrocarbon oil of lubricating viscosity. As synthetic oils there can be mentioned alkylated waxes ,and similar alkylated hydrocarbons of relatively high molecular weight, hydrogenated polymers 'of hydrocarbons; and theconden sation products or chl'orinatedalkylhydrocarbons with ethyl compounds. 'Other suitable oils are those which are obtained by polymerization of lowermolecular'weight alkylene oxides such as propylene and/or ethylene oxide. Stillother synthetic oils areobtained by 'etherifica'tio'n' and/or este'rification of the hydroxy groups amylase oxide polymers such as, for example, the acetate of the z-ethylhexanol-initiated polymer of propylene oxide". Other important classes of synthetic oils include the variousesters as, for example,

l'di U-ethylhexyl)sebacate,fltricresyl phosphate arid silicate esters. If desired, the oilcan'be a mixture of mineral and syhth'etic oils. 3 I I ,While satisfactory lubricant compositions can be 'obi n fbt dihs name Oil emb y n ne 6r more of the polymeric additives of the type described above, it alsofalls within the urview (if this invention to provide lubricant compositions which contain not only such such polymers, but also other additives such as pour point depressants, oiline'ss and extreme pressure agents, anti-oxidants, corrosion inhibiting agents, blooming agents, thickening agents, and/or compounds for enhancing the temperature-viscosity characteristics of the oil.

The present invention'also contemplates the addition to the lubricant composition (particularly when the amount of copolymer em w ea'is relatively small) of auxiliary detergents and/or anti-wear agents. g

Illustrative lubricant compositions of the above type containing the copolymeric additives of the invention in combination with'other agents may include, for example, from about'0.1 to 10% by weightof alkaline earth metal higher alkylphenate detergent and wear reducing agents such'as calcium alkylphenates having anaverage of approximately 14 carbon atoms in the alkyl group as well organic thiophosphate corrosion and high temperature oxidation inhibitors such as the reaction product of pin'ene and P 8 and the bivalent metaldihydrocarbyl dithiophosphates, zinc butyl hexyl dithiophosphate and zinc tetradecylphenyl dithiophospliate .in amounts of from about 0. 1 to- 1 0% by weig'ht'ot the composition. Temperature-viscosity improvingagents which may be employed in the tamponsa usually in amounts of from about 1 to 10% by weight, include by way of example the homopolymers of alkylmethacrylates such as the dodecyl methacrylate polymers known to the .trade as Acryloid 710 and Acryloid 763; products of Rohm &

Haas Company, and highmolecular weight butene polymers such as Paratone ENJ 15P, a product of the Eui y p ys V The eflicacy 'of'polymeric additives of the type described above as detergents and anti-Wear agents in lubricating oils is illustrated by data'from a number of tests. In the tests from which the data is obtained, the base oil, unless otherwise specified, is asolvent-refined, wax-free SAE-30 grade rnineral lubricating oil havinga viscosity index of which is derivedfrom California waxy crude. Various amounts of the polyr'nericadditivesare incorporated in the oil as noted in'terr ns of percentby weight.

In the lacquer 'd esitien test the-16w temperature detergency of the oils tested is measured by determining the ability of the oil to solubilize and retain typical engine fuel deposits and precursors thereof which are formed due to incomplete combustion of the fuel. Retention of these deposits in a given oil depends upon their dispersal and upon minimizing their polymerization to lacquer.

Briefly described, the lacquer deposition test involves condensing fresh cool flame oxidation products from a standard test fuel simulating the fuel combustion products of an internal combustion engine in a steel vessel containing a certain amount of the lubricating oil being tested. The steel surface of the vessel acts as an iron catalyst for polymerization of the fuel oxidation products to lacquer in the same manner as the steel surfaces in an internal combustion engine. After the oxidation products have been condensed, the steel vessel containing the lubricating oil is heated for 24 hours at a temperature selected to correspond with actual engine conditions. The test oil is then decanted while hot from the lacquer deposits formed in the steel vessel due to polymerization and the lacquer deposits are de-oiled and weighed.

In the actual test a low grade gasoline is employed of the type described in connection with the standard FL-2 test procedure given below. The gasoline at a rate of 13.3 cc. per hour is vaporized and mixed with air, the air rate being 1.75 liters per minute. The vapor mixture of gasoline and air is then fed into an elongated cool flame combustion chamber of standard design having a diameter of 1 /2 inches. The cool flame combustion chamber is maintained at 695 F. The test is continued for 1 hour during which the oxidation products issuing from the cool flame combustion chamber are condensed into the weighed steel catalyst vessel which contains 30 g. of the oil being tested at about room temperature. The steel vessel containing test oil and condensed oxidation products is then heated for 24 hours at 110 F. The oil is decanted from the lacquer deposits in the vessel, following which the deposits are de-oiled by washing with petroleum solvent. The increase in weight of the steel vessel due to the lacquer deposits is then determined and recorded in milligrams as LD or lacquer deposit.

The lacquer deposit for any given lubricant composition obtained in accordance with the procedure described above is directly correlated to the piston varnish rating or PVR obtained for the same lubricant composition in the standard FL-2 test procedure previously referred to and hereinafter more particularly described. Table II which follows gives the correlated values for both the lacquer deposits and piston varnish ratings.

Table II LD PVR LD PVR The correlated values in the above table provide an accurate means for estimating from the lacquer deposits determined for a given oil the piston varnish rating to be obtained in the standard FL-2 Chevrolet engine test.

In the test where the piston varnish ratings are obtained, a given lubricating oil composition is tested as the crankcase lubricant in a 6-cylinder Chevrolet engine using a low grade gasoline especially prone to cause engine deposits, the conditions being those defined in the standard FL-2 test procedure as described in the June 21, 1948, report of the Coordinating Research Council. This procedure requires the maintenance of a jacket temperature of 95 F. and a crankcase oil temperature of F. at 2500 r.p.m. and 45 brake horsepower of 40 hours, and therefore closely simulates the relatively cold" engine conditions which are normally experienced in city driving. At the end of each test, the engine is dismantled and the amount of engine deposits on the piston determined and expressed as the piston varnish rating. This value is obtained by visually rating (on a scale of O to 10, with 10 representing the absence of any deposit) the amount of deposit on each piston skirt and averaging the individual ratings so obtained for the various pistons. Under the conditions of this test, a piston varnish rating of 4.5 is indicative of satisfactory performance, though preferably this rating should be 5 or above. The wear experienced by the piston rings during the test is also measured in certain cases and expressed in mgs. of metal lost per hour. 5 mgs. per hour is regarded as satisfactory, though preferably the loss should be 3 mgs. or less per hour. In the case of the base oil alone without the addition of any additives it is found that the piston varnish rating is approximately 3.0 and the piston ring weight loss is 5.5 mgs./hr. On the other hand, as indicated by the data presented in the tables below, when the base oil is compounded with the indicated amounts of a copolymer, greatly superior results are obtained.

In the tables which follow, Table III gives the test data showing piston varnish ratings of various lubricant compositions and Table IV gives the test data showing lacquer deposit.

Table III Piston varnish rating Lubricant composition Base oil alone 3. 0 1.5% copolymer of (1) dodccyl methacrylate, (2) methacrylic acid and (3) nonaethylene glycol methacrylate in base oil 1.5% copolyrner of (l) dodecyl methacrylate, (2) methacrylic acid and (3) nonaethylene glycol methacrylate in base oil 1.5% copolymer of (l) dodecyl methacrylate, (2) methacrylic acid and (3) dodecylether of decaethylene glycol methacrylate in base 011.. 1.5% copolymer of (1) tridecyl methacrylate, (2) octadecyl methacrylate, (3) methacrylic acid and (4) octadecylether of eicosaethylene glycol methacrylate in base oil 3.6% copolymer of (1) tridecyl methacrylate,

(2) octadecyl methacrylate and (3) dodecylether of decaethylene glycol methacrylate in base oil 1 0.8% copolymer of (1) tridecyl methacrylate,

(2) octadecyl methacrylate and (3) dodecylether of dooctacontahekataethylene glycol methacrylate in base oil 2 0.8% copolymer of (1) tridecyl methacrylate,

(2) octadecyl methacrylate and (3) dodecylether of triheptacontadohekataethylene glycol methacrylate in base oil 2 1.5% copolymer of (l) heptaisobutylene phenoxyethyl methacrylate, (2) methacrylic acid and (3) dodecyletherdecaethylene glycol methacrylate in base 011 1.5% copolymer of (1) dodecyl methacrylate, (2) methacrylic acid and (3) methoxy (mixed polyethylene glycol-polypropylene glycol in approx. 1:1 mole ratio having an av. mol. wt. of approx. 400) methacrylate in base oil 1.5% copolymer of (1) dodecyl methacrylate, (2) methacrylic acidand (3) octapropylene glycol methacrylate in base oil 1.5% copolymer of (l) dodecyl methacrylate,

(2) methacrylic acid and (3) decylthlononaethylene glycol methacrylate in base oil 1.5% copolymer of (1) dodecyl methacrylate, (2) acrylic acid and (3) methacrylate of dodecyl monoether of decaethylene glycol (Av. Mol. Wt. 440) in base oil 1.5% copolymer of (l) (alkylphenoxy)*-ethyl methacrylate, (2) methacrylic acid and. (3) methacrylate of lauryl monoether of polyethylene glycol (Av. Mol. Wt. 440) in base oil. 1.5% copolymer of (1) dodecyl methacrylate,

(2) methacrylic acid, (3) heptadecenyl-2-hydroxyethyl imidazoline methacrylate and (4) dodecyl ether of decaethylene glycol methacrylate in base oil 1.2% copolymer of (1) tridecyl methacrylate,

(2) octadecyl methacrylate. (3) methacrylamide and (4) tridecyl ether of decaethylene glycol methacrylate in base oil Table III-Continued minutes. If no coagulation occurs, 2 cc. of glacial acetic acid is added and the time to the first coagulation oi Ratio of (l) monomerto Pistqn asphalt 1S recorded. The results of the asphaltene test Lubricant com osition monomer varmsh correlate W1th the piston varnish rating and the lacquer to (3) monomer, rating 5 Em depos t for the polyglycol addit ves as noted above. Wlth the base oils alone coagulation occurs immediately. C a 2,. copolymer of (1) dodecyl mcthacrylate, agulation times of 30 minutes or more indicate etfective (2) allyl stem-ate, (3) mono(metl1oxy dodi 6 t de'caethylene glycol )maleate and (4) maleic SP rsan 5- mhYdnde base 011 In the examples whlch follow, ldentlcal polymerlzatlon Prepared by alkylating phenol with polybutylene (Av. 014 per molecOnd1t1onS v,Vere employed m preparation of the polycu le) over BF; catalyst. k glycol addltlves unless otherwise noted. Average molecutggfg ggg ggggg ggg and 18 mmumles per lar Weights were obtained from viscosity measurements.

150 Neutral mineral lubricating oil, 27 millimoles per kg. calcium allgyl phenate sull'urized having an average of 13 carbon atoms per alkyl EXAMPLE v1 grqu derived irompropylene olymer, l2 millimoles per kg. zine butyl- 15 he dtthiophospha'te and 5.7 0 Acryloirl 703.

- l This example illustrates a. typical preparation of, the

Table IV 1 I copolymer of dodecyl methacrylate. wlth dodecyl ether! Ratio of (l) Lacquer capped polyethylene glycol (1600 mol. wt.) methacrylate Lubricant com osltton monomer to (2) deposit P monomerw (3) (mm and its evaluation as a dispersant.

o grams) Into a 500 cc. three-necked fiask equipped with mechanical stirrer, reflux condenser, and buret was charged Base ollalone" 850 23% copolymer of (1) dodecylmethacrymey 106 g. dodecyl methacrylate (0.418 mole), 14 g. dodecyl 2 mono(dodecylo q7) hexadecaethylene ether-capped polyethylene glycol (1600 mol. wt.) meth- 40/1/1 450 25 y f .007.? mole) and 213 g. benzene. 0.01% econ g; gzp iy g azodnsobutyronltnle was then charged. The polymer zal' A 1 l. '1 t 65. glg' o na g l t n t) tion was run at reflux after sweeping out the system with. figg l methacrylamlde 24/1/1/1 286 nitrogen. Reaction temperature was 88 C. ma azodi- (;7)1 l2g{ (igtrlilkaclglmeg fl y g isobutyronitrile was added in increments every 15 minutes 00 ecy I116 act-ya e, me 8- cryllc acid, 4) trldecyl ether oihexadecato maintain a constant catalyst v lethyleneglycolmethacrylate,and(5) Conversion 111 7 /2 hours was 86%. The, product had dtethylamlnoethyl methacrylate in base nil 1 H d d th 1 t 14 10/1 1/1 244 an alkyl to dodecyl ether-capped polyethylene glycol 2.87 copo ymer o 1 o ecy me acrya e,

g mdec} ether Qf methylene glycol (1600 mol. wt.) methacrylate ratio of 88.1, and 2.8? m l fi fi and (3) ethylene glycol 150 neutral gave a vlscoslty of 267 SSU at 100 F. monomethacrylate in base oil 14/1/1 160 o and 58.2 SSU at 210 F. It had an average molecular The utility of still other lubricant compositions in acf 0f appfoxlmately The isPhaltene 1 cordance with the invention in which various representae s hourstive oils of lubricating viscosity are employed is illus- EXAMPLE. VII trated by the additional examples given in the following 40 tabl This example shows. the copolymerlzatlon of dodecyl Table V Ratio of (1) mono- B mer to (2) Visgggity vitscfisgy Viscioslty L t ase oil monomer a a ln ex ubrlcnnt compost ion to SSU U monomer, etc.

Base oil alone Mixed hexyloctyl orthosilicate 45. 2 33. 5 183 2.8% copolymer of (1) octadecene, (2) di-Z-ethylhexyl fumarate, do 10/15/3/1 47. 5 34.3 210 (3) crotonic acid and (4) tridecylether of decaethylene glycol methacrylate in base oil. Base oil alone Ogtyloxyoetapropylene glycol acetate- 86. 6 39. 8 170 2.8% copolymer of (1) hexene, (2) dodecyl methacrylate, (3) do 17/25/2/4 128.6 47.7 170 methacrylic acid and (4) dodccylether oi octadcca thylene glycol methacrylate in base oil. Base oil alone.. Dioctylphthalate 138.8 40.3 10 8% copolymer of (1) hexene, (2) dodecyl rnethaerylate, (a) "was 17/25/2/4 256.1 53.3 125 metbucrylic acid and (4) dodecylether oi octadecaethylene glycol methaerylate in base oil.

From the tests of the foregoing table it will be seen that each of the illustrative compositions containing the copolymeric lubricating oil additives according to the invention possess improved lubricating properties compared to the base oils alone.

The outstanding dispersant properties of the polyglycol macromolecular additives of the invention are also illustrated by the following examples showing their efficacy in the standard asphaltene test.

In the asphaltene test 5 cc. of a 5% solution of the dry polyglycol polymeric additive is mixed with 2 cc. of a 1% solution of airblown Midway Asphalt in benzene. The mixture is diluted to 25 cc. with n-pentane. This diluted mixture is shaken up and observed for two methacrylate, dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate, and N-vinyl pyrollidone.

. 21 '210 F. 58.1 SSU V.I. 142 Average molecular weight 280,000 Asphaltene test, 1% hours.

EXAMPLE VIII This example shows the copolymerization of dodecylmethacrylate, dodecyl ether-capped polyethylene glycol 1600 mol. wt.) methacrylate, and 4-vinyl pyridine.

Charge:

106 g. dodecyl metha'crylate 13.5 g. dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate .1.8 g. 4-vinyl pyridine (0.017 mole) 209 g. benzene Catalyst level 0.008% Conversion in 8 hours was 92.5% Nitrogen content 0.06% nitrogen Ratio 102:1:1.04 2.8% in 150 neutral gave vis. at

100 F. 256 SSU 210 F. 57.2 SSU V.I. 140.5 Average molecular weight 270,000 Asphaltene test, 2% hours.

EXAMPLE IX This example shows the copolymerization of dodecyl methacrylate, dodecyl ether-capped-polyethylene glycol (1600 mol. wt.) methacrylate, and glycidyl methacrylate.

Charge:

106 g. dodecyl methacrylate 13.5 g. dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate 2.4 g. glycidyl methacrylate (0.017 mole) 209 g. benzene Catalyst level 0.008% Conversion in 8 hours was 90.5% Viscosity at 100 F. 246 SSU 210 F. 57.0 SSU VI. 143 Ratio 142:l:5.8 Average molecular weight 260,000 Asphaltene test, 2 hours.

EXAMPLE X This example shows the copolymerization of dodecyl methacrylate, dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate and N,N-diethyl-aminoethyl methacrylate.

Charge:

106 g. dodecyl methacrylate V A 13.5 g. dodecyl ether-capped-polyethylene glycol (1600 mol. wt.) methacrylate g 1.2 g. N,N-diethylaminoethyl methacrylate (0.0065 mole) 210 g. benzene Catalyst level 0.008% Conversion in 8 hours was 93% Nitrogen content 0.045% nitrogen Ratio 143:1:1.23 2.8% in 150 neutral gave vis. at

100 F. 255 SSU 210 F. 56.8 SSU V.I. 140 Average molecular weight 250,000 Asphaltene test, 2 hours.

EXAMPLE XI This example shows copolymerization of dodecyl methacrylate with methacrylamicle initiated polyethylene glycol.

EXAMPLE XII This example shows copolymerizationof dodecyl methacrylate, dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate, and methacrylarnide.

Charge:

106 g. dodecyl methacrylate (0.418 mole) 13.5 g. dodecyl ether-capped polyethylene (1600 mol. wt.) methacrylate 1.5 g. methacrylamide (0.0217 mole) v 209 g. benzene Catalyst level 0.008% a Conversion in 8 hours was 86.5%

Nitrogen content 0.175% nitrogen Ratio :1:3.5 T

2.8% in neutral gave vis. at

100 F. 221 SSU 210 F. 53.6 SSU V.I. 141

Average molecular weight. 180,000

Asphaltene test 1 hour and 20 minutes.

EXAMPLE XrII v i This example shows copolymerization of dodecyl methacrylate, dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate, and N-vinyl carbazone.

glycol Charge: 1 v 106 g. dodecyl methacrylate (0.418 mole) 13.5 g. dodecyl ether-capped polyethylene glycol v 1600 11101. wt.)-n1ethacrylate i 1.79 g. N-vinyl carbazole (0.009 mole) 209 g. benzene. Catalyst level 0.006% Conversion in 8 hours was 98% Ratio 86:1:1.2 2.8% in 150 neutral gave vis. at

100 F. 299 SSU 210 F. 63.7 SSU V.I. 144, Average molecular weight 440,000 Asphaltene test, greater than 2% and less than 18 hours.

. EXAMPLE XIV This example shows copolymerization of dodecyl methacrylate, dodecyl ether-capped polyethylene glycol 1600 'mol. wt.) methacrylatqand 'acrylonitrile.

Charge:

106 g. dodecyl methacrylate 13.5 g. dodecyl ether-capped polyethylene glycol (1600 mol. wt.) methacrylate 2.4 g. acrylonitrile (0.045 mole) 208 g. benzene Catalyst level 0.006% Conversion in 8 hours was 88% Ratio 132:1:1.6 2.8% in 150 neutral gave vis. at

' 100 F. 221 SSU 210 F. 53.5 SSU g3 V.I. 140.5 ge mol cular igh .9.000 Asphaltene. test, 40 minutes.

EXAMPLE xv This example shows copolymerization of dodecyl methacrylate with diethylamine initiated polyethylene glycol 2000 methacrylate.

Charge: 114 g. dodecyl methacrylate 6 g. diethylamine initiated polyethylene glycol (2000) methacrylate (0.0027 mole) 213 g. benzene Catalyst level 0.008% Conversion in 8 hours was. 91.5% Nitrogen content 0.08% Ratio 61:1 2.8% in 150 neutral gave vis. at

100 F. 302 SSU; 210- F. 61.7 SSU VI. 1395. Average molecular weight 380,000 Asphaltene test, greater than 48 hours.

' EX MPLE X This example. shows: the copolymerization of dodecyl methacrylate with: allylamineinitiated polyethylene glycol (750 mol. wt.) to provide an effective. dispersant.

The method of polymerization was as in the above examples. The charge was 40 g. allylamine initiated polyethylene glycol (750; WL), (0.0251mol'e), 20 g. do! decyl methacrylate (0.079 mole) and 108: g. benzene. Catalyst level was 0.015%. azobisisobutylnitrile. 60 g. dodecyl methacrylate and 108 g-.. benzene were added over five hours. The polymerization was run for eight hours. Conversion was 82%. To the reaction mix was added 100 g. of 150 neutral mineral lubricating oil1and. the benzene was, distilled off. Threevolmnes of mixed hexanes were added. The. mixture was stirred at 130 F. for four hours, allowed to stand overnight, and the insolubles were separated by centrifiigation to dehaze the mixture. The monomer ratio after this dehazingwas 135 to 1'. The asphaltene test showed the copolymer as having dispersing properties.

EXAMPLE XVII The copolymer of dodecyl methacrylate with polyethylene glycol (1600. mol. wt.). vinyl ether, is illustrated in this example.

Into a 500 cc. three-necked flask equipped with. me chanical stirrer, reflux condenser and buret' was added 100 g. dodecyl methacryl'ate, (;395"mole g. polyethylene glycol (1600 mol. wt.) vinyl ether, (0.0111mole), and 0.01% azobisisobutylnitiile. The; flask'was" flushed with nitrogen, and polymerization was run; at: reflux. A benzene solution of azobisisobutylnitrile' was added at 15-minute intervals to maintain catalyst level. Conversion in eight hours was 67%. Polyethylene glycol analysisindicated an alkyl to polyglycol ratio of 94 to 1. Asphaltene test was more than. 7. hours.

EXAMPLE. XVIII This example; illustrates. the polyglycol polymers in which the. 1 polyglycol chains. are. attached. to. a preformed polyisobutylene backbone via phosphonyloxy groups.

300 cc. of an 11.6% solution oi polyisobutylene (mol. wt. about 200,000) in benzenewasv mixed with cc. phosphorus trichloride. Oxygen was blown through the solution at 10-20 C. untilevolution. of, heat ceased. The chlorophosphonylated" polymer was. purified by repeated precipitation from benzene with, acetone. Yield 86%. 9 g. of this product in 75 ml, benzene was re fluxed 3 hours with 5 ml. pyridine and 25. g. dried, basefree dodecyl ether-capped polyethylene glycol (mol. wt. about 1800). The product thus obtained was, purified by precipitation from benzene with methanol.

The dried polymer product, upon analysis, was found to contain 0.34, 0.37% phosphorus corresponding to approximately 117 isobutylene units per glycol phosphonate group. The average molecular weightwas estimated as 60,000. 2.8% of the polymer in 150 neutral mineral lubricating oil had the following viscosity-temperature characteristics:

Vis. F. 2.19.7 SSU Vis. 210 F. 49.17 SSU V.I. 114 Asphaltene test: Greater than 5 hours.

EXAMPLE XIX Polyglycolmacromolecules in which the polyglycol group is attached by means of sulfonyloxy group to a polyisobutylene backbone are shown. by' this example.

10. g. polyisobutylene (mol. wt. about 200,000) and 0.25 g. a,a' azobisisobutyronitrile were dissolved in cc. benzene and saturated with sulphur dioxide gas at 60 C. The gas was introduced at 1 liter per minute, through a fritted disc in; the bottom of the vessel. Chlorine was bubbled in through a tube above this disc at about 1.25 liter per minute for 10 minutes. The solution was flushed with dry nitrogen and was added to. 25 g. dodecyl ether-capped polyethylene glycol (mol. wt. about 1800) and 5 cc. pyridine in 150 cc. chloroform. The mixture was boiled gently until the volume was reduced to 150 cc. total.

The polymer obtained abovev was purified by repeated precipitation with methanol. The yield of polymer was 7.2%.. Thedried. polymer was analyzed and' found to contain 1.43, 1.41% sulphur. The average molecular weight was 160,000. 2.8% of the polymer in 1.50 neutral mineral lubricating oil' had the following viscosity temperature characteristics:

Vis. 100 F..481-.3.SSU Vis. 210 F. 76.47 SSU V.I. 132

Asphaltene test: 1 hour.

This application is a continuation-in-part of Stuart,

Stewart, Lowe and Kavanagh patent application Serial No. 574,635, filed March 29, 1956, now abandoned, which in turuis. acontinuation-in-partof Stuart, Stewart, Lowe, and. Kavanagh patent application. Serial No. 400,757, filedlDecember 28, 1953, now abandoned, Lowe,-

Stewart, Stuart, and Kavanagh patentapplication Serial.

No. 400,758, filed December 28, 1953, now abandoned, and Stewart, Stuart, Lowe, and Kavanagh patent application Serial No. 400,759, filed December 28,, 1953, now abandoned.

This application is also a continuation-in-part of Lowe, Stuart, Stewart and Kavanagh patent application Serial No. 645,887, filed March 14, 1957, now abandoned, and Stewart, Lowe, Stuart and Kavanagh patent application Serial No. 645,88, filed March 14, 1957, now abandoned, and Lowe, Stuart, Stewart and. Kavanagh patent application Serial No. 646,524, filed March 18; 1957', now abandoned.

We claim:

1. A lubricant composition comprising. a major'portion of an oil of lubricating viscosity'and a minor portion suflicient to enhance the detergent characteristics of the composition of an oil-soluble polyglycol substituted poly mer of at least one monomer, said monomer containing of polyglycol groups, said oil-solubilizing groups being selected from the class consisting of aliphatic and cycloaliphatie hydrocarbon groups of at least 4 carbon atoms each, said polyglycol groups being selected from the class consisting of polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alkylene group and a molecular weight between about 220 and 30,000, said polymer being substantially saturated and having a total molecular weight of at least about 50,000 and a solubility in oil of :at least 0.5% by weight, said polyglycols having at least alkylene oxide units each and being attached by a single thermally stable organic linking group to said polymer.

2. A lubricant composition according to claim 1 in which the polyglycol is polyethylene glycol.

3. A lubricant composition according to claim 1 in which the polyglycol is polypropylene glycol.

4. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion suflicient to enhance the detergent characteristics of the composition of an oil soluble polyglycol substituted polymer of at least one monomer of the class consisting of olefins of from 2 to 30 carbon atoms, unsaturatedethers and unsaturated esters, said monomer containing a single polymerizable ethylenic bond and said polymer containing from about 40 to about 96% by weight of hydrocarbon oil-solubilizing groups from said polymerized monomer and from about 4 to about 60% by weight of polyglycol groups, said oil-solubilizing groups being selected from the class consisting of aliphatic and cycloaliphatic hydrocarbon groups of at least 4 carbon atoms each, said polyglycol groups being selected from the class consisting of polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alkylene group and a molecular weightbetween about 220 and 30,000, said polymer being substantially saturated and having a total molecular weight of at least about 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each and being attached by a single thermally stable organic linking group to said polymer.

5. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition of an oil-soluble polyglycol substituted poly mer of at least one monomer, said monomer containing a single polymen'zable ethylenic bond and said polymer containing from about 40 to about 96% by weight of hydrocarbon oil-solubilizing groups from said polymerized monomer and from about 4 to about 60% by weight of polyglycol groups, said oil-solubilizing groups being selected from the class consisting of aliphatic and cycloaliphatic hydrocarbon groups of at least 4 carbon atoms each, said polyglycol groups being selected from the class consisting of polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alkylene group and a molecular weight between about 220 and 30,000, the polyglycol groups each being linked to said polymer by a single thermally stable organic linking group selected from the class consisting of alkylene groups of from 1 to 7 carbon atoms each, oxy(O-), carbonyl 26 and imino(NH) groups and combinations thereof with alkylene'groups of from 1 to 7 carbon atomseach, said polymer being substantially saturated and having a total molecular weight of at least about 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each.

6.'A lubricant composition comprising a major portion of anoil of lubricating viscosity and a minor'portion, sufficient to enhance the detergent characteristics of the composition, of an oil-soluble polymer of mono mers, selected from at least each of the first two classes of the classes consisting of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from'4 to 30 aliphatic carbon atoms, (B) at least one ester of a,fi-ethylenically unsaturated monocarboxylic acids of from 3 to 15 carbon atoms each, in which the alkyl groups contain from 1 to 4 carbon atoms each, the carboxylgroups of said acids being monoester-linked to a member of the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, and (C) acidic compounds selected from the group consisting of a,fl-ethylenica lly unsaturated monocarboxylic acids of from 3 to 15 carbon atoms each, in which the alkyl groups contain from 1- to 4 carbon atoms each, a,,8-ethylenically unsaturated apdicarboxylic acids of from 4 to 12 carbon atoms each, in which the alkyl groups. contain from 1 to 4 carbon atoms each, anhydrides and monoesters of said dicarboxylic acids with an alcohol selected from the group consisting of polyalkylene glycols and ethers thereof asdefined in (B) and aliphatic hydrocarbon alcohols of from 8 to 30 carbon atoms, said (A) component constituting from about 40 to 96% by weight mole percent and said (B) and (C) components constituting from about 4 to 60% by weight of thepolymer composition, there being present at least 4% by weight of said (B) component, said polymer having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene units each.

7. A lubricant composition according to claim 6 in which the polyglycol substituted polymer has as an addi-. tional component the monomer N-vinyl pyrollidone.

8. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion, suflicient to enhance the detergent characteristics of the composition, of an oil-soluble polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms, (B) at least one ester of a,fl-ethylenically unsaturated monocarboxylic acids of from 3 to 15 carbon atoms, in which the alkyl groups contain from 1 to 4 carbon atoms each, the carboxyl groups of said acids being monoester-linked to-a member of the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monolkyl ethers thereof, and (C) acidic compounds selected from the group consisting of a, 3-ethylenically unsaturated monocarboxylic acids of from- 3 to 15 carbon atoms each, in which the alkyl groups containing from 1 to 4 carbon atoms each, a,fi-ethylenically unsaturated a,fi-dicarboxylic acids of from 4 to 12 carbon atoms each, in which the alkyl groups contain from 1 to 4 carbon atoms each, anhydrides thereof and monoesters of said dicarboxylic acids with an alcohol selected from the group consisting of polyalkylene glycols and ethers thereof as defined in (B) and aliphatic hydrocarbon alcohols of from 8 to 30 carbon atoms, said (A) component constituting fi'om about 40 to 96% by weight and'said (B) and (C) components constituting from about 4 to 60% by weight of the polymer composition, there being present at least 4% by weight of said (B) component-a'nd said polymer having a molecular weight of at 27 least. 50,000- and' a, solubility in oil of. at least 0.5% by weight, said polyglycols having at least 5 alkylene units each.

9 A. lubricant composition comprising a major portion; t an oil, of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition, of an oil-soluble polymer of (A) polymerizable' oil-solubilizing compounds having a single ethylenic linkage and'containinga monovalent hydrocarbongroup of from 4 to 30 aliphatic carbon atoms and B),- at least. one ester ofi m, 3-ethylenically unsaturated monocarboxylic acids of' from} to 15 carbonatoms, in

which-the.- alkyl groups contain from l to 4 carbon atomseach, thecarboxyl, groups of said acids being monoesterlinked. to a-member of the group consisting of: polyalkylene glycols having; a molecular weight between about 220 and 30,000. and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, said (A) component constituting from about 40 to 96% by weight and said (B) components constituting a total of from about 4m 60%. by weight of the polymer composition, there being presentat-least one monomer of said (B) component and said polymer having a molecular weight of atleast 50,000 anda solubility in oil of atleast 0.5%, byweight, said n lyglycols having; at least 5' alkylene oxide units. each.

1 0.v A lubricant composition comprisingamajor per.- tion of. mineral. lubricating oil and a minorportion, sufficient to enhance the detergent characteristics of the-composition,, of. an oil-soluble. polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing amonovalent hydrocarbon group, of from 4 to 30 aliphatic carbon atoms, (B) at least one ester of u,}3-ethylenically unsaturated monocarboxylic acids ofifrom 3 to. carbon atoms, in which-thealkyl groupscontairr from 1 to 4 carbonatomseach, the carboxyl= groups of said acids being monoester-linked. to a member of the groupconsisting of polyalkylene-1 glycols havinga molecular weight-between about 220' and.3.0,-0.00 and from. 2 tof 7 carbon; atoms; in each. alkylene; group andmonoalkyl-ethersthereof, and (C); acidic. compounds selected from the-group consisting. of fi-ethylen'ically unsaturatedmonocarboxylic acids; of from. 3 to 15 carbon atoms each, in which the; alkyl groups contain from 1 to 4 carbon atoms each, a,fl-ethylenically unsaturated a,;3-' dicarboxylic acids-.offrom 4 to 12'. carbon atoms each, in. which; the alkyl groups contain from 1 to 4 carbon atoms each,. anhydrides thereof: and. monoesters of said dicarboxylic acids with an alcohol selected from the group consisting of polyalkylene. glycols. and ethers thereof as defined in (B.-) and' aliphatic hydrocarbon alcohols of from 8'1t0. 30. carbon. atoms, said (A) component constituting;from about 40 to 96% by weight and. said- (B). and (C3); components. constituting from about 4: to. 60% by. weight of*thepolymer composition, there being'presentl atleast' 4% by weightof said (B component. and said polymer-having amolecular-weight of at least 50,000 and a-solubility'in. oil: ofi at least 0.5% by: weight,- said polyglycols. having at least 5 alkylene oxide units each.

11. A lubricant composition comprising'a major portionof mineral lubricating oil and a minoriportion; .suf.-. ficient to enhance the.detergent'characteristics ofthe composition, of an oil-solublepolymer of A) polymerizable oil-solubilizing. compounds having a single etliylinic" link age and containing a-monoval'ent hydrocarbon group of from 4to=30 aliphatic carbon atoms and (B) atleast one esterof a,p3'-ethylenica-lly unsaturated monocarb'oxylic acids of from 3 to 15" carbon atoms, in which'the alkyl groups containfrom 1' to 4 carbon atoms'each, the car boxyl" groupsof said; acids. being monoester-linkedI to a member of'the. group consisting. of polyalkylene glycols havingaimolecular weight betweenabout 220 and- 3.0', 0.00 and from-v 2 to. 7 carbon atoms in each. alkylenegroup and monoalkyl ethers, thereof, said (A) componentconstituting, from aboutv 40 to.9 6.% byweight: and.saidi(B.).

component constituting-- a. total of from about 4 to. 60% by weight of the polymer composition, there'being presout at least one monomer of said (B) component and saidpolymer. having a, molecularweight of at least 50,000 and a solubility inl oil of at least 0.5 %l by' weight, said polyglycols: having; at-least. 5- alkylene oxide units each.

12.. A lubricant. composition comprising a major portion of mineral lubricating oil and from about 0.1 to 10% by weightof an oil soluble polymer of (A) polymerizableoil-solubilizing compounds having a single ethylenic linkage andcontaining: a monovalenthydrocarbon group'oif front- 4 to 3.0 aliphatic carbon atoms, (B) at least one ester of e,fl-ethylenically unsaturated monocarboxylic acids ofzfrom 3- to 15 carbon atoms, in which the alkyl groups containafrom- 1- to 4 carbon atoms each, the carboxyl groups of said acids being monoester-linked to a member of the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30g000 andfrom 2' to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, and. (C) acidic compounds selected from the group consisting of p ethylenical ly unsaturated. monocarboxylic acids of from 3 to 15 carbon atoms each, in which the alkyl groups contain from.- I to. 4 carbonatoms each, a,fi-ethylenically unsaturated;a,p=dicarboxylic. acids of from 4 to 12 carbon atoms. each, in,whieh. the, alkyl groups contain from 1. to 4.- carbonatoms each, anhydrides thereof and monoesters of said dicarboxylicacids with an alcohol selected from the group consisting of polyalkylene glycols and ethers thereof as defined in (B) and aliphatic hydrocarbon alcohols of from 8 to 30: carbonatoms,- said (A) component constituting from about 4010 96% by weight and said (B) and (C) components constituting from about 4 to--60% by weight ofthe polymer composition, there being present at least 4% by weight of said (B) component and saidpolyrner having a molecular-weight of at least. 50,000 andiarsolubility' in oil of at least 0.5 by; weight; said polyglycolszhaving-at'least 5 alkylene oxide units: each.

13. A lubricant. composition comprising a major portion of mineral lubricating oil and from about 0.1- to 10%. by weight of: an oil-soluble polymer of (A) polymerizable oil-solubilizing compoundshaving a single ethylenic linkage and containinga monovalent hydrocarbon group of from 4 to.;30 aliphatic carbon atoms and (B) at. least one ester. of a,;3.-ethylenically unsaturated monocarboxylic acids offrom 3-to 1'5carbon atoms, in which the alkyl groups' containfrom 110 4 carbonatoms each,

the carboxyl groups of said acids being monoester-linked to amember of the group consisting of polyalkylene glycolshaving a molecular weight between about 220 and 30,000 and from-'2 to 7 carbonatoms in each alkylene group and;monoalkyl ethers thereof, said (A)-component constituting'frorn about. 40. to 96% by. weight and said (B) component constituting a total of from about 4 to 60% by. weightv of the polymer composition, there being present at leastone-monomer of said. (B) component and said polymerhaving-amolecular weight of at least 50,000 and asolubility in. oil of atfleast 0.5% by weight, said polyglycolsliavingat least 5 alkylene oxide units each.

14. A.lubricant.compositionaccording to claim 13 in which the polyglycol is polyethylene glycol and there is included from about 0.1 to 10% by weight of. an oilsoluble alkaline earth metal alkyl phenate.

15'.- A lubricantzcomposition-according to claim 13 in which the polyglycol is polyethylene glycol and there is included from about 0.1 to 10% by weight of an organic thiophosphate corrosion. and high temperature oxidation inhibitor.

16. An addition agent capable of imparting enhanced detergent and antiwear characteristics to a lubricating oil consisting essentially of'anoilof lubricating viscosity and from about l0=to by weight of an oil-soluble polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic; carbon atoms, (B) at least one ester of a,fi-ethylenically unsaturated monocarboxylic acids of from 3 to 15 carbon atoms, in which the alkyl groups contain from 1 to 4 carbon atoms each, the carboxyl groups of said acids being monoester-linked to a member of the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, and (C) acidic compounds selected from the group consisting of a,f3-ethylenically unsaturated monocarboxylic acids of from 3 to 15 carbon atoms each, in which the alkyl groups contain from 1 to 4 carbon atoms each, a, 3-ethylenically unsaturated a,,8-dicarboxylic acids of from 4 to 12 carbon atoms each, in which the alkyl groups contain from 1 to 4 carbon atoms each, anhydrides thereof and monoesters of said dicarboxylic acids with an alcohol selected from the group consisting of polyalkylene glycols and ethers thereof as defined in (B) and aliphatic hydrocarbon alcohols of from 8 to 30 carbon atoms, said (A) component constituting from about 40 to 96% by weight and said (B) and (C) components constituting from about 4 to 60% by Weight of the polymer composition, there being present at least 4% by weight of said (B) component and said polymer having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each. A

17. An addition agent capable of imparting enhanced detergent and antiwear characteristics to a lubricating oil consisting essentially of an oil of lubricating viscosity and from about to 75% by weight of an oil-soluble polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms and (B) at least one ester of fi-ethylenically unsaturated monocarboxylic acids of from 3 to carbon atoms, in which the alkyl groups contain from 1 to 4 carbon atoms each, the carboxyl groups of said acids being monoester-linked to a member of the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, said (A) component constituting from about 40 to 96% by weight and said (B) components constituting a total of from about 4 to 60% by weight of the polymer composition, there being present at least one monomer of said (B) component and said polymer having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each.

18. A lubricating composition comprising a major portion of a mineral lubricating oil and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) an alkyl methacrylate having an alkyl group of from 8 to 30 carbon atoms, (B) esters of methacrylic acid wherein the carboxyl group of said acid is monoester-linked to polyethylene glycols having an average molecular weight between about 400 and 10,000 and (C) methacrylic acid, said (A) component constituting from about 40 to 96% by weight and said (B) and (C) components constituting from about 4 to 60% by weight of the polymer composition, there being present at least 4% by weight of said (B) component, and said polymer having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5% by weight.

19. A lubricating composition comprising a major portion of a mineral lubricating oil and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) an alkyl methacrylate having an alkyl group of from 8 to 30 carbon atoms and (B) esters of mcthacrylic acid wherein the carboxyl groups of said acid are monoester-linked to monoalkyl ethers of polyethylene glycols having an average molecular weight between about 400 and 10,000, said (A) component constituting from about 40 to 96% by weight and said (B) component constituting from about 4 to 60% by weight of the polymer composition, there being present at least one monomer of said (B) component and said polymer having a molecular weight'of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each.

20. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition of an oil-soluble polymer of monomers selected from at least each of the first two classes of the classes consisting of (A) polymerizable oil-solubilizing esters having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 8 to 30 aliphatic carbon atoms, (B) esters selected from the group consisting of monoesters and diesters of a,fi-ethylenically unsaturated u,B-dicarboxylic acids of from 4 to 12 carbon atoms each in which the alkyl groups contain from 1 to 4 carbon atoms each and wherein the carboxyl groups of said acids are monoester-linked to a member of the group consisting of aliphatic alcohols of from 8 to 30 carbon atoms and polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, only one of the terminal hydroxyl groups of said polyalkylene glycols being ester-linked to said carboxyl groups and at least one of said monoester-linked members being said polyalkylene glycol, and (C) acidic compounds selected from the group consisting of u,}3-ethylenically unsaturated monocarboxylic acids of from 3 to 15 carbon atoms each, in which the alkyl groups contain from 1 to 4 carbon atoms each and a,B-ethylenically unsaturated a,,B-dicarboxylic acids of from 4 to. 12 carbon atoms each, anhydrides and monoesters of said dicarboxylic acids, the alcohol portion of the ester group being aliphatic hydrocarbon containing from 8 to 30 carbon atoms, said oilsoluble polymers having from 40 to 96% by weight of the oil-solubilizing component (A) from 4 to 60% by weight of components (B) and (C), amolecular weight of at least 50,000 and a solubility in oil of at least 0.5 by weight, there being present at least 4% by weight of said (B) component and said polyglycols having at least 5 alkylene oxide units each.

21. A lubricant composition comprising a major portion of an oil of lubricating viscosity and from about 0.1 to 10% by weight of an oil-soluble'polymer of (A) a polymerizable oil-solubilizing ester having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 8 to 30 aliphatic carbon atoms, and (B) esters selected from the group consisting of monoesters and diesters of a,fl-ethylenically unsaturated a,fi-dicarboxylic acids of from 4 to 12 carbon atoms each in which the alkyl groups contain from 1 to 4 carbon atoms each and wherein the carbonyl groups of said acids are monoester-linked to a member of the group consisting of aliphatic alcohols of from 8 to 30 carbon atoms and polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alkylene group and a molecular weight between about 220 and 30,000 only one of the terminal hydroxyl groups of said polyalkylene glycols being ester-linked to said carboxyl groups and at least one of said monoester-linked members being said polyalkylene glycol, said oil-soluble polymers having a molecular weight of at least 50,000, from 40 to 96% by weight of the oil-solubilizing component (A), from about 4 to 60% by weight of component (B) and a solubility in oil of at least 0.5 by weight, said polyglycols having at least 5 alkylene oxide units each.

22. A lubricant composition comprising a major portion of an oil of lubricating viscosity and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) a polymerizable oil-solubilizing ester having a single ethylenic linkage and containing a'monovalent hydrocarbon group of from 8 to 30 aliphatic carbon atoms,

(B) esters selectedfrom thegroup consisting: of mono esters and diesters of a,B-ethylenically unsaturated (1,5- dicarboxylic acids of. from 4 to' 12. carbon atoms each in which the alkyl groupsv contain from 1 to 4 carbon atoms each and wherein the carboxyl groups of said acids are monoester-linked to a member: of the group consisting of aliphatic alcohols of from 8 to 30 carbon atoms and polyethylene glycols having a molecular weight between about: 220 and 30,000, only one of the terminal. hydroxyl groups of said polyethylene glycols be ng linked:to said carboxylgroupsand at least one of said monoester-linked members being said polyethylene glycol, and (C) acidic compounds selected from the group consisting of w,/3-ethylenically' unsaturated monocarboxylic acids of from 3' to carbon atoms each in which the alkyl groups contain from 1 to 4 carbon atoms each, a,fl-ethylenicallyunsaturated 0:,[3-(liCfl1bOXY1iC acids of from to 12 carbon atoms each in which the alkyl groups contain from 1 to 4 carbon atoms each, anhydrides and monoesters of said dicarboxylic acids, the alcohol portion of the ester group being aliphatic hydrocarbon containing from 8 to 30 aliphatic carbon atoms, said oil-soluble polymers having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A) from about. 4 to 60% by weight of components (B) and (C) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by Weight of said (B) component.

23. A lubricant composition comprising a'major portion of an oil of lubricating viscosity andfrom about 0.1 to 10% by weight of an oil-soluble polymer of (A) dodecyl met-hacrylate, (B) mono(dodecyloxy) hexadecaethylene glycol maleate and (C) maleic anhydride, said oil-soluble polymers having a molecular weight of at least 50;000, from about 40 to 96% by weightof the oil-solubilizing component (A), from about 4 to 60% by' weight of components (B) and (C) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component.

24. A lubricant composition comprising a major portion of an oil of lubricating viscosity and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) a mixture ofallyl stearate and dodecyl methacrylate, (B) mono(methoxy dodecaethylene glycol) maleate and (C) maleic auhydride, said oil-soluble polymers having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A) from about 4 to 60% by weight of components (B) and (C) and'a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component.

25. A lubricant composition comprising a major portion of an oil of lubricating viscosity and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) a mixture of dodecyl methacrylate" and allyl stearate, (B) mono-methoxy dodecaethylene glycol) maleate and (C) maleic anhydride, said. oil-soluble polymers having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A), from about 4 to 60% by weight of components (B) and (C) and a solubility in oil of at least 0.5 by weight, there being present at least 4% by weight of said (B) component.

26. A lubricant composition comprising a major portion of an oil of' lubricating viscosity and a minor portionsufiicient to enhance the detergent characteristics of the. compositionv of anIoilvsoluble'polymer of monomers selected from at least each. of the first three classes of the classes consisting of (A) polymerizable oil-solubilizing compounds having; a single ethylenic linkage and containing a monovalent hydrocarbon group of from 8 to 30 aliphatic carbon atoms, (B) esters of acidic compounds selected from the group consisting of a a-ethylenically unsaturated monocarboxylic acids of from 3' to 8 carbon atoms each and" diestersof a,p-ethylenically unsaturated a,fl-dicarboxylic acids of from 4 to 12' carbon atoms each in which the alkyl groups contain. from 1 to 4 carbon atoms each and whereinthe carboxyl groups of said acidic compounds are monoester-linked to av member of the group consisting ofpolyalkylene glycols having from 2 to 7 carbon atoms ineach alkylene-group and monoalkyl others-thereof, said polyalkylene glycolshaving a molecular weight between about 220 and 30,000, (B) esters of unsaturated carboxylic acids of from. 3 to 15 carbon. atoms wherein the carboxyl groups of said acidic compounds aremonoester-linked' to an alkyl alcohol of not more than 7 carbon atoms wherein at least 50% of the carbon atoms therein and not less than two thereof are attached to polar groups selected from the group consisting of hydroxyl and aminogroups, and (C) unsaturated carboxylic acids of from 3 to 15 carbon atoms each, said oil-soluble polymer having a molecular weight of at least 50,000, from about 40 to96% by weight of the oil-solubilizing component (A), from about 4'to 60% by weight of components (3), (B) and (C) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said ('B) component and said polyglycols having atleast 5 alkylene oxide units each;

27. A lubricant composition comprising a major portion. of a mineral lubricating oil and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) dodecyl methacrylate, (B) tridecyl ether of decaethylene glycol monomethacrylate and (B) ethylene glycol monomethacrylate; said oil-soluble copolymer having a molecular weight of at least 50,000, from about 40 to 96% by weight of theoil-solubilizing component.(A) from about 4m 60% by weight of the- (B) and (B) componentsand a solubility in oil of at least 0.5 by weight, therebeing present at least 4% by weight of said (B) component.

28; A lubricant composition comprising a major portion of an oil of lubricating-viscosity, together with from 0.1. to l'0.%by weight, of a polymer of (A) ahigher. alkyl ester of an a,B-ethylenically unsaturated monocarboxylic acid. of from 3 to 8' carbon atoms in which the alkyl groupcontains from 8 to 30 carbon atoms, (B) esters of an a,fl-ethylenically unsaturated monocarboxylic acid of from 3 to- 8 carbon atoms each wherein the carboxyl groups. of said monocarboxylic acid are monoester-linked to a polyethylene glycol having an average molecular weight between about 400 and 10,000, and (B) esters ofv the monocarboxylic acids as defined in (B) wherein the carboxyl groups of said monocarboxylic acids are monoester-linked' to an alkyl polyhydric alcohol of not more than 7 carbon atoms, said polymer havinga molecular weight of atv least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A), from about 4 to 60% by weight of the (B) and (B) components and a solubility in-oil of at least 0.5 by weight, there. being present at least 4% by weight. of said (B) component.

29. A lubricant composition comprising a major portion of an oil of. lubricating viscosity, together with from 0.1 to 10% by weight, of a polymer of (A) a higher alkyl. ester of an a,;3-ethylenically unsaturated monocarboxylic acid of from 3 to 8 carbon atoms in which the-alkyl group contains from 8 to 30 carbon atoms, (B) esters of'an a,fi-ethylenically unsaturated monocarboxylic acid of from 3 to 8 carbon atoms each wherein the carboxyl groups of said monocarboxylic acid are monoester-linked to a. polyethylene glycol. having an average molecular weight betweenabout1400 and 10,000, and (B) esters of the monocarboxylic'acids as defined in (B) wiherein'the carboxyl groups of said monocarboxylic acids are monoester-linked to an aliphatic amino-alcohol of not more than 7 carbon atoms, said copolymer having a molecular weight of at least 50,000 and from about 40 to 96% by weight of the oil-solubilizing component (A), from about-4 to 60% by weight. of components '33 (B) and (B'),- and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component.

30. The composition of claim 29, wherein the polyethylene glycol is the tridecyl monoether of hexadecaethylene glycol and the aliphatic alcohol is N,N-diethyl aminoethyl alcohol.

'31. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition of an oil-soluble polymer of monomers selected from at least each of the first three classes consisting of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms, (B) esters of acidic compounds selected from the group consisting of a,B-ethylenically unsaturated monocarboxylic acids of from 3 to "8 carbon atoms each and a, 8-ethylenically unsaturated, a,fi-dicarboxylic acids of from 4 to 12 carbon atoms each in which the alkyl groups contain from 1 to 4 carbon atoms each and wherein the carboxyl groups of said acidic compounds are monoester-linked to a member of the group consistingof polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alkylene group and a' molecular weight between about 220 and 33,00, (C) polymerizable compounds selected from the group consisting of amides, monovalent hydrocarbon amidesQmonovalent hydrocarbon amine salts and substituted monovalent hydrocarbon amides and amine salts of unsaturated carboxylic acids of from 3 to 15 carbon atoms wherein the substituent on said substituted monovalent hydrocarbon group is at least one polar group selected from the group consisting of hydroxyl and amino groups and the monovalent hydrocarbon group is an alkyl group of not more than 7 carbon atoms, (D) unsaturated carboxylic acids of from 3 to 15 carbon atoms, said oil-soluble polymer having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A), from about 4 to 60% by weight of components (B), (C) and (D) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component and said polyglycols having at least 5 alkylene oxide units each.

32. A lubricant composition comprising a major portion of a mineral lubricating oil and from about 0.1 to by weight of an oil-soluble polymer of (A) dodecyl methacrylate, (B) tridecyl ether of decaethylene glycol methacrylate, (C) N-Z-hydroxyethyl methacrylamide and (D) acrylic acid, said oil-soluble polymer having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oil-solubilizing component (A), from about 4 to 60% by weight of components (B), (C) and (D) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component.

33. A lubricant composition comprising a major portion of a mineral lubricating oil and from about 0.1 to 10% by weight of an oil-soluble polymer of (A) dodecyl methacrylate, (B) dodecyl ether of decaethylene glycol methacrylate, (C) heptadecenyl-2-hydroxyethyl imidazoline methacrylate, and (D) methacrylic acid, said oilsoluble polymer having a molecular weight of at least 50,000, from about 40 to 96% by weight of the oilsolubilizing component (A), from about 4 to 60% by weight of components (B), (C) and (D) and a solubility in oil of at least 0.5% by weight, there being present at least 4% by weight of said (B) component.

34. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition of an oil-soluble polyglycol substituted polymer of olefins of from 2 to 30 carbon atoms, said polymer containing from about 40 to about 96% by weight of hydrocarbon oil-solubilizing groups from 34 said polymerized olefins and from about 4 to about 60% by weight of polyglycol, groups, said oil-solubilizing groups being selected from the class consisting of aliphatic and cycloaliphatic hydrocarbon groups of at least 4., carbon atoms each, said polyglycol groups being selected from the class consisting of polyalkylene glycols and monoalkyl ethers thereof having from 2 to 7 carbon atoms in each alky-lene group and a molecular weight between about 220 and 30,000, said polymer being substantia-lly saturated and having a total molecular weight of at least about 50,000 and a solubility in oil of at least 0.5 by weight and said polyglycol groups being attached by a single su-lfonyloxy group to the polymer, said polyglycols having at least 5 alkylene oxide units each.

35. A lubricant composition according to claim 34 in which the olefin is isobutylene and the polyglycol is polyethylene glycol.

36. A lubricant composition according to claim 34 in which the olefin is isobutylene and the polyglycol is polypropylene glycol.

37. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion, suflicient to enhance the detergent characteristics of the composition of an oil-soluble polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms and (B) at least one monoalkenyl ether of a polyalkylene glycol selected from the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000 and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, said alkenyl group having not more than 20 carbon atoms, said (A) component constituting from about 40 to 96% by weight and said (B) component constituting a total of from about 4 to 60% by weight of the polymer composition, there being present at least one monomer of said (B) component and said polymer being substantially saturated and having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least 5 alkylene oxide units each and being attached by a single oxy other group to said polymer.

38. A lubricant composition according to claim 37 in which the compound (A) is alkyl methacrylate wherein the alkyl group contains from 8 to 30 carbon atoms and the polyglycol alkenyl ether of component (B) is vinyl ether of polyethylene glycol.

39. A lubricant composition according to claim 37 in which the compound (A) is alkyl methacrylate wherein the alkyl group contains from 8 to 30 carbon atoms and the polyglycol alkenyl ether of component (B) is vinyl ether of polypropylene glycol.

40. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufiicient to enhance the detergent characteristics of the composition, of an oil-soluble polymer of (A) polymerizable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms and (B) at least one N-alkenyl amino alkyl ether of a polyalkylene glycol selected from the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000, and from 2 to 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, said alkenyl group having from 3 to 20 carbon atoms and said amino alkyl group having from 2 to 7 carbon atoms, said (A) component constituting from about 40 to 96% by weight and said (B) component consisting a total of from about 4 to 60% by Weight of the polymer composition, there being present at least one monomer of said (B) component and said polymer being substantially saturated and having a molecular Weight of at least 50,000 and a solubility in oil of at least 0.5% by weight, said polyglycols having at least alkylene oxide units each and being attached by a single amino' group to said polymer.

41. A lubricant composition according to claim 40 in which the (A) component is alkyl methacrylate wherein the alkyl group contains from 8 to 30 carbon atoms and the N-alkenyl ether is N-allyl amino ethyl monoether of polyethylene glycol.

42. A lubricant composition according to claim 40 in which the (A) component is alkyl methacrylate wherein the alkyl group contains from 8 to 30 carbon atoms and the N-alkenyl ether is N-allyl amino propyl monoether of polypropylene glycol.

43. A lubricant composition comprising a major portion of an oil of lubricating viscosity and a minor portion sufficient to enhance the detergent characteristics of the composition, of an oil-soluble polymer of (A) polymer-izable oil-solubilizing compounds having a single ethylenic linkage and containing a monovalent hydrocarbon group of from 4 to 30 aliphatic carbon atoms and (B) at least one ethylenically unsaturated acyl amido alkyl ether of a polyalkylene glycol selected from the group consisting of polyalkylene glycols having a molecular weight between about 220 and 30,000, and from 2 t0 7 carbon atoms in each alkylene group and monoalkyl ethers thereof, said acyl group having from 3 to 20 carbonatoms and saidamido alkyl group having from 2 to 7 carbon atoms, said (A) component constituting from about'40 to 96% by weight and said (B) component constituting a total of from about 4 to 60% by weight of the polymer composition, there being present at least one monomer of said (B) component and said polymer being substantially saturated and having a molecular weight of at least 50,000 and a solubility in oil of at least 0.5 by weight, said polyglycols having at least 5 alkylene oxide units each and being attached by a single amido group to said polymer.

'44. A lubricant composition according to claim 43 in which the (A) component is alkyl methacrylate wherein the alkyl group contains from'8 to carbon atoms and the acyl amido alkyl ether of-polyalkylene glycol is methacrylamido ethyl monoether of polyethylene glycol.

45. A 'lu'bricant composition according to claim 43 in which the -(A) component is alkyl methacrylate wherein the alkyl group contains from 8 to 30 carbon atoms and the acyl amido alkyl ether of polyalkylene glycol is methacrylamido propyl monoether of polypropylene glycol.

Edmonds May 14, 1957 Cashman et al Feb. 25, 1958 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,892,783 June 30, 1959 Frank A. Stuart et 31.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 11, lines152 to 54, the formula should appear as shown below instead of as in the patent:

Z p -T column 15, line 59, for 20: 2: 5 read -20 7 5; column 16, line 35, strike out suc first occurrence; column 22, line 42, for carbazone read carbazole; column 24, line 62;, for Serial N 0. 645,88 read -Serial No. 645,888; column 26, line 59, for monolkyl read monoa1kyl; column 31, line 56, for mono-methoxy read -mono (methoxy-; column 33, line 27, for 933,00, read -30,000,; column 34, line 75, for consisting read constituting.

Signed and sealed this 26th day of April 1960.

Attest: KARL H. AXLINE, ROBERT C. WATSON, Attesting Ofiaer, Ganwm'saiomr of Patents. 

1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PORTION OF AN LUBRICATING VISCONITY AND A MINOR PORTION SUFFICIENT TO ENHANCE THE DETERGENT CHARACTERISTICS OF THE COMPOSITION OF AN OIL-SOLUBLE POLYGLYCOL SUBSTAINED POLYMER OF AT LEAST ONE MONOMER, SAID MONOMER CONTAINING A SINGLE POLYMERIZABLE ETHYLENIC BOND AND SAID POLYMER CONTAINING FROM ABOUT 40 TO ABOUT 90% BY WEIGHT OF HYDROCARBON OIL-SOLUBILIZING GROUPS FROM SAID POLYMERIZED MONOMER AND FROM 4 TO ABOUT 60% BY WEIGHT OF POLYGLYCOL GROUPS, SAID OIL-SOLUBILIZINNG GROUPS BEING SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC AND CYCLOALIPHATIC HYDROCARBON GROUPS OF AT LEAST 4 CARBON ATOMS EACH, SAID POLYGLYCOL GROUPS BEING SELECTED FROM THE CLASS CONSISTING OF POLYALKYLENE GLYCOLS AND MONOALKYL ETHERS THEREOF HAVING FROM 2 TO 7 CARBON ATOMS IN EACH ALKYLENE GROUP AND A MOLECULAR WEIGHT BETWEEN ABOUT 220 AND 30,000, SAID POLYMER BEING SUBSTANTIALLY SATURATED AND HAVING A TOTAL MOLECULAR WEIGHT OF AT LEAST ABOUT 50,000 AND SOLUBILITY IN OIL OF AT LEAST 0.5% BY WEIGHT, SAID POLYGLYCOLS HAVING AT LEAST 5 ALKYLENE OXIDE UNITS EACH AND BEING ATTACHED BY A SINGLE THERMALLY STABLE ORGANIC LINKING GROUP TO SAID POLYMER.
 5. A LUBRICANT COMPOSITION COMPRISISNG A MAJOR PORTION OF AN OIL OF LUBRICATING VISCOSITY AND A MINOR PORTION SUFFICIENT TO ENHANCE THE DETERGENT CHARACTERISTICS OF THE COMPOSITION OF AN OIL-SOLUBLE POLYGLYCOL SUBSTITUTED POLYMER OF AT LEAST ONE MONOMER, SAID MONOMER CONTAINING A SINGLE POLYMERIZABLE ETHYLENIC BOND AND SAID POLYMER CONTAINING FROM ABOUT 40 TO ABOUT 96% BY WEIGHT OF HYDROCARBON OIL-SOLUBILIZING GROUPS FROM SAID POLYMERIZED MONOMER AND FROM ABOUT 4 TO 60% BY WEIGHT OF POLYGLYCOL GROUPS, SAID OIL-SOLUBILIZING GROUPS BEING SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC AND CYCLOALIPHATIC HYDROCARBON GROUPS OF AT LEAST 4 CARBON ATOMS EACH, SAID POLYGLYCOL GROUPS BEING SELECTED FROM THE CLASS CONSISTING OF POLYALKYLENE GLYCOLS AND MONOALKYL ETHERS THEREOF HAVING FROM 2 TO 7 CARBON ATOMS IN EACH ALKYLENE GROUP AND A MOLECULAR WEIGHT BETWEEN ABOUT 220 AND 30,000, THE POLYGLYCOL GROUPS EACH BEING LINKED TO SAID POLYMER BY A SINGLE THERMALLY STABLE ORGANIC LINKING GROUP SELECTED FROM THE CLASS CONSISTING OF ALKYLENE GROUPS OF FROM 1 TO 7 CARBON ATOMS EACH, OXYL(-0-), CARBONYL 